CN110961085B - By using CO2Method for preparing amidoxime functionalized hollow porous polymer microspheres for emulsion template - Google Patents
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Abstract
By using CO2A method for preparing amidoxime functionalized hollow porous polymer microspheres for an emulsion template. The invention belongs to the technical field of adsorption separation functional materials, and relates to CO2A method for preparing amidoxime functionalized hollow porous adsorbent by using the amidoxime functionalized hollow porous adsorbent as an emulsion template; the method comprises the following steps: firstly, preparing silicon dioxide nano particles and MF-HP; adding MF-HP and PEA into ethanol, performing ultrasonic and water bath reaction, washing with water, washing with ethanol, and drying to obtain MF-NH2Adding HP into a glutaraldehyde aqueous solution, performing water bath, water washing, alcohol washing and drying to obtain MF-CHO-HP, adding the MF-CHO-HP and DAMN into an ethanol solution, performing water bath, water washing, alcohol washing and drying to obtain MF-CN-HP, adding hydroxylamine hydrochloride into a mixed solution of water and ethanol, reacting, and performing water washing, alcohol washing and drying to obtain MF-AO-HPS; the invention provides possibility for subsequent modification of a large number of action sites by grafting PEA, and the PEA is combined with a hollow porous structure, so that the adsorption capacity of U (VI) adsorption is improved, and the mass transfer dynamics is accelerated.
Description
Technical Field
The invention belongs to the technical field of preparation of adsorption separation functional materials, and particularly relates to CO2A method for preparing amidoxime functionalized hollow porous adsorbent by using the amidoxime functionalized hollow porous adsorbent as an emulsion template.
Background
Due to the particular use in the nuclear industry, the naturally occurring uranium resource has become a strategic resource in the nuclear industry. The uranium resources that have been explored are mainly present in the seawater in the form of hexavalent uranium (u (vi)), about 45 million tons, that is, seawater is a potential source of uranium resources. The extensive use of uranium is severely limited due to the relative difficulty in extracting it in large quantities from seawater. Furthermore, the presence of uranium in seawater is not only hazardous to humans and the environment, but also dangerous due to the radioactive and chemical toxicity of the uranium. Therefore, the uranium extracted from the seawater not only has economic value, but also has environmental protection and scientific development significance. There are various methods for extracting U (VI) from seawater, such as electrodialysis, extraction, chemical precipitation, organic-inorganic ion exchange, and adsorptive separation, etc. As a mature technology, an adsorption method having advantages of high adsorption efficiency, low preparation cost, low secondary pollution generation, simple operation, and the like has been widely used for extracting uranium from seawater. However, extraction of uranium from seawater has been faced with significant challenges, including low concentrations (about 3.3ppb), the presence of large quantities of competing ions, and complex chemical and biological environments. In order to effectively extract U (VI) from seawater, the development of an environment-friendly, high-selectivity and high-efficiency adsorbent is urgently needed.
There are various types of adsorbents for ion extraction, and among them, hollow porous adsorbents (HPS) have been receiving much attention because of their low density, definite structure, and strong carrying capacity. The Pickering emulsion template method is one of the most common methods for preparing hollow porous adsorbents. Due to the special spatial configuration of the amidoxime group, the amidoxime group can coordinate with U (VI) to achieve the effect of selective adsorption. By utilizing the principle, amidoxime groups can be modified on the surface of the material to endow the material with the capability of selectively adsorbing U (VI).
The use of the conventional Pickering emulsion template method generally has the disadvantages that the inner phase elution process is complicated and the use of an organic solvent causes serious environmental problems, the control of the size is limited, the size is large, and the like. The functional monomer directly participates in polymerization, so that a large number of functional sites are positioned in the polymer, the mass transfer rate is low, and unnecessary loss is caused because a part of the functional sites cannot participate in the reaction. In order to avoid the above disadvantages, it is necessary to research a new material for selectively extracting uranium.
Disclosure of Invention
Aiming at overcoming the defects of the prior art, the invention aims to solve the problems that the inner phase is difficult to elute and the structure is difficult to control in the preparation of the existing Pickering emulsion template method, and the like, and provides a method for preparing a hollow porous adsorbent by using an amidoxime functional water-in-gas emulsion template method.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
(1) preparing silicon dioxide nano particles;
adding a certain amount of tetraethyl orthosilicate (TEOS) into ethanol, heating in water bath, heating, and dropwise adding a certain amount of NH3·H2A mixed solution of O and water; then reacting the formed mixed solution for a period of time under magnetic stirring; after the reaction is finished, centrifugally collecting a product, washing the product for three times by using deionized water and ethanol respectively, and drying the product to obtain silicon dioxide nano particles;
(2) preparing hollow porous melamine resin;
dispersing the silica nanoparticles obtained in the step (1) in deionized water to obtain silica aqueous dispersion; then, under a certain temperature condition, adding melamine into a mixed solution of a formaldehyde solution and a glutaraldehyde solution, adjusting the pH value of the mixed solution, stirring, and continuing to react for a period of time after the solution is changed from milky white to clear; after the reaction, adding the silicon dioxide aqueous dispersion under the stirring condition for reaction; cooling to a certain temperature after reaction, adjusting the pH value again, reacting, performing polymerization reaction under a water bath condition after reaction, finally, collecting a product by centrifugation, washing with deionized water and ethanol, and drying to obtain a powder sample; adding the powder sample into hydrofluoric acid solution for etching, centrifuging, collecting the product, washing with deionized water and ethanol, centrifuging again, collecting the product, and drying to obtain hollow porous melamine resin, which is recorded as MF-HP;
(3) dispersing the MF-HP and polyethylene Polyamine (PEA) prepared in the step (2) in ethanol to obtain a mixed solution A, then carrying out ultrasonic treatment, and placing the mixed solution A under the condition of magnetic stirring in a water bath for reaction; centrifuging after reaction, washing the obtained product with ethanol, centrifuging again and collecting the product to obtain the hollow porous melamine resin polymer microsphere with the surface grafted with amino, and marking as MF-NH2-HP; then MF-NH2Adding HP and glutaraldehyde into ethanol to obtain a mixed solution B, and then placing the mixed solution B under the condition of magnetic stirring in a water bath for reaction; after the reaction is finished, washing the product with deionized water and ethanol respectively, and centrifugally collecting to obtain hollow porous melamine resin polymer microspheres with aldehyde groups grafted on the surfaces, wherein the hollow porous melamine resin polymer microspheres are marked as MF-CHO-HP;
(4) suspending the MF-CHO-HP and Diaminomaleonitrile (DAMN) prepared in the step (3) in 40-60mL of ethanol E to obtain a mixed solution C, then carrying out ultrasonic treatment, and placing the mixed solution C under the condition of magnetic stirring in a water bath for reaction; centrifuging after reaction to obtain hollow porous melamine resin with the surface grafted with nitrile groups, and marking as MF-CN-HP; finally, adding ethanol F into deionized water to obtain a mixed solution of ethanol water, adding MF-CN-HP and hydroxylamine hydrochloride into the mixed solution, adjusting the pH value, and then placing the mixture under a water bath condition for reaction; and centrifuging after reaction, collecting a product, washing with deionized water and ethanol, and drying to obtain the amidoxime functionalized hollow porous melamine resin microsphere, which is recorded as MF-AO-HPS.
Using the same procedure as in step (3), except that MF-CHO-HP was replaced by MF-HP, another adsorbent without grafted PEA was obtained, denoted as MF-nPEA-AO-HPS.
Preferably, the tetraethyl orthosilicate in the step (1), ethanol and NH3·H2The dosage ratio of O to water is 8.0-10 g: 170-190 mL: 9.0-11 mL: 9.0-10g, the reaction temperature is 30-40 ℃, and the reaction time is 2.0-4.0 h.
Preferably, the certain temperature condition in the step (2) is 80-90 ℃.
Preferably, the dosage ratio of the melamine, formaldehyde and glutaraldehyde mixed solution to the silicon dioxide dispersion liquid in the step (2) is 1.0-2.0g:2.0-4.0mL:5.0-15 mL; the volume fraction of the formaldehyde solution is 37 percent, and the volume fraction of the glutaraldehyde solution is 25 percent; the concentration of the aqueous silica dispersion was 10 wt%.
Preferably, the pH adjustment in step (2) is performed using Na2CO3Adjusting the pH value of the solution to 9.0-10.0; the Na is2CO3The concentration of the solution was 2.0M.
Preferably, the stirring condition in the step (2) is 1200-1600 rpm; the continuous reaction is carried out for 3.0-5.0 min; the time for adding the silicon dioxide aqueous dispersion to carry out reaction is 10-30 min.
Preferably, the cooling in the step (2) is carried out to a certain temperature of 30-50 ℃; the operation of adjusting the pH again is as follows: dropwise adding HCl with the concentration of 2.0M to adjust the pH value to 5.0-6.0; the time for carrying out the reaction after the pH is adjusted again is 10-30 min.
Preferably, the temperature of the water bath in the step (2) is 30-50 ℃; the time of the polymerization reaction is 3.0 to 5.0 hours; the volume concentration of the hydrofluoric acid solution is 2%; the drying temperature is 60-80 ℃.
Preferably, the MF-HP, the polyethylene polyamine and the ethanol in the step (3) are used in a ratio of 0.3-0.5mg:3.0-5.0 g: 40-60 mL.
Preferably, the time of the ultrasonic treatment in the step (3) is 5.0-10 min; the temperature of the water bath of the mixed solution A is 30-40 ℃, and the reaction time is 8.0-16 h.
Preferably, the MF-NH in step (3)2-the ratio of the amounts of HP, glutaraldehyde and ethanol is between 0.2 and 0.4 mg: 8.0-12 mL: 30-50 mL; the volume fraction of glutaraldehyde was 25%.
Preferably, the temperature of the water bath of the mixed solution B in the step (3) is 20-30 ℃, and the reaction time is 8.0-16 h.
Preferably, the MF-CHO-HP, diaminomaleonitrile and ethanol E are used in the step (4) in a ratio of 0.2-0.6mg:0.4-1.2 mg: 40-60 mL.
Preferably, the ultrasonic treatment time of the mixed solution C in the step (4) is 5.0-10min, the water bath temperature is 20-30 ℃, and the reaction time is 2.0-4.0 h.
Preferably, the volume ratio of the ethanol F to the water in the step (4) is 9: 1; the dosage ratio of the mixed solution of MF-CN-HP, hydroxylamine hydrochloride, ethanol F and water is 0.2-0.6mg: 2.0-6.0 g: 40-60 mL.
Preferably, the pH adjustment in step (4) is performed by adjusting the pH to 8.0-9.0 with 1.0M NaOH; the temperature of the water bath is 70-90 ℃, and the reaction time of the water bath is 4.0-8.0 h.
Preferably, the temperature of the drying in the step (4) is 60-80 ℃.
Where ethanol E and ethanol F are both ethanol, the letters E and F are merely for the distinction of expressions.
The invention has the beneficial effects that:
(1) the invention selects selective ligand with amidoxime group as U (VI), takes hollow porous melamine resin as a substrate, and utilizes an air-in-water emulsion template method to prepare the hollow porous adsorbent (MF-AO-HP) with amidoxime functionalized on the surface, thereby realizing the specific adsorption of U (VI).
(2) The hollow porous melamine resin polymer microspheres with surfaces rich in aldehyde groups are prepared by an air-in-water emulsion template method, so that the U (VI) diffusion path is shortened, the mass transfer dynamics is improved, the aldehyde groups contained in the microspheres avoid the phenomena of unstable combination and the like caused by subsequent modification, and the preparation process is simplified; grafting by PEA offers the possibility of modification of high density of action sites; the high-density amidoxime sites grafted on the surface of the MF-AO-HP can interact with a large amount of U (VI), so that the adsorption capacity of the adsorbent is improved, and the MF-AO-HPS and the MF-nPEA-AO-HPS have higher adsorption capacity than the MF-nPEA-AO-HPS on the U (VI) under different pH conditions through the experimental results of pH response.
Drawings
FIGS. 1 a and b are SEM images of MF-HP prepared in example 1; c and d are TEM images of MF-HP prepared in example 1.
FIG. 2 shows MF-HP and MF-NH prepared in example 12IR spectra of-HP, MF-CHO-HP, MF-CN-HP and MF-AO-HPS.
FIG. 3 shows MF-HP, MF-NH prepared in example 12Zeta potential profiles of HP, MF-AO-HPS and MF-nPEA-AO-HPS.
FIG. 4 a is the XPS spectrum of the MF-AO-HPS prepared in example 1; b is the C1s high resolution spectrum of MF-AO-HPS prepared in example 1; c is the high resolution spectrum of N1s of MF-AO-HPS prepared in example 1.
FIG. 5 shows MF-HP and MF-NH prepared in example 12Analysis of organic elements for-HP, MF-CHO-HP, MF-CN-HP and MF-AO-HPS.
FIG. 6 is a solid NMR carbon spectrum of MF-AO-HPS prepared in example 1.
FIG. 7 is a thermogravimetric analysis of MF-AO-HPS prepared in example 1.
FIG. 8 is a graph of the effect of pH on the adsorption capacity of MF-AO-HPS, MF-nPEA-AO-HPS and MF-HP as prepared in example 1.
FIG. 9 shows the adsorption kinetics of MF-AO-HPS prepared in example 1 and its model-fitted curve.
FIG. 10 is a graph of the effect of temperature on the adsorption equilibrium of the MF-AO-HPS prepared in example 1 for uranyl ions and a model fit curve thereof.
FIG. 11 shows the selective adsorption capacity of MF-AO-HPS prepared in example 1.
FIG. 12 shows the adsorptive regeneration performance of the MF-AO-HPS prepared in example 1.
Detailed Description
The identification performance evaluation in the embodiment of the invention is carried out according to the following method: this was done using static adsorption experiments. Measuring the adsorption capacity of 2.0mg of MF-AO-HPS, MF-nPEA-AO-HPS and MF-HP for U (VI) in the pH range of 3.0-9.0, measuring the content of U (VI) after adsorption by using an inductively coupled plasma emission spectrometer, and determining the optimal adsorption pH according to the result; to study the maximum adsorption capacity of MF-AO-HPS, we performed adsorption equilibrium experiments at U (VI) concentrations ranging from 10 to 500mg/L, fitted the adsorption data using Langmuir and Freundlich models, and calculated the adsorption capacity based on the results; after saturated adsorption, other substances with the same structure as uranyl ions are selected as competitive adsorbates to participate in the research of the selective adsorption performance and the adsorption regeneration performance of the MF-AO-HPS.
The invention is further illustrated by the following examples.
Example 1:
(1) preparing silicon dioxide nano particles;
use of
Method for manufacturing silica nanoparticles: in a flask, 8.735g of TEOS was added to 180mL of ethanol, heated to 35 ℃ in a water bath, and 10mL of NH was added dropwise3·H2A mixed solution of O and 9.48g of water; then reacting the formed mixed solution for 3.0h under magnetic stirring; after the reaction is finished, centrifuging and collecting a product, and washing the product for three times by using deionized water and ethanol respectively; drying to obtain silica nanoparticles with the diameter of 180-200 nm;
(2) preparing hollow porous melamine resin;
1.26g of melamine was added to 3.0mL of a mixed solution of 37% formaldehyde and 25% glutaraldehyde (v/v, 2: 1) at 85 deg.C, and then 2.0M Na was used2CO3Adjusting the pH value of the solution to 9.5, stirring at 1500rpm, and continuing to react for 3.0min after the solution is changed from milky white to clear; subsequently, 10mL of 10 wt% aqueous silica dispersion was added under stirring, and the reaction was continued for 20 min; then, cooling the solution to 40 ℃, dropwise adding 2.0M HCl to adjust the pH value to 5.5, continuing to react for 20min, stopping stirring, and polymerizing for 4.0h under the condition of 40 ℃ water bath; finally, collecting a product through centrifugation, washing with deionized water and ethanol, and drying to obtain a powder sample; adding the obtained powder into 2% HF solution at room temperature for etching, centrifuging to collect the product, washing with deionized water and ethanol for three times respectively, centrifuging again to collect the product, and drying at 60 deg.C to obtain hollow porous melamine resin, which is marked as MF-HP;
(3) MF-AO-HPS can be obtained by the following method: first, 0.4g of MF-HP powder and 4.0g of PEA were dispersed in 50mL of ethanol in a flask, followed by sonication for 5.0 min. Subsequently, the resulting mixture was reacted for 12 hours under magnetic stirring in a water bath at 35 ℃; then, the product is collected by centrifugation and washed with ethanol for three times to obtain the hollow porous melamine resin polymer microsphere with the surface grafted with amino, which is marked as MF-NH2-HP; secondly, 0.4g of MF-NH2-HP, 10mL of 25% GA and 40mL of ethanol mixture were added to the flask and then reacted for 12h under magnetic stirring in a water bath at 35 ℃; after the reaction is finished, washing the product with water for 3 times to remove excessive GA, then washing with ethanol for 2 times, and centrifugally collecting the hollow porous melamine resin polymer microspheres with aldehyde groups grafted on the surfaces, wherein the hollow porous melamine resin polymer microspheres are marked as MF-CHO-HP;
(4) suspending 0.4g MF-CHO-HP and 0.8g DAMN in 50mL ethanol, performing ultrasonic treatment for 5.0min, and reacting at 25 ℃ for 3.0h under magnetic stirring; then collecting the product to obtain hollow porous melamine resin with the surface grafted with nitrile groups, and marking as MF-CN-HP; finally, 0.4g of MF-CN-HP and 4.0g of NH were added2OH HCl in 50mL H2In a mixed solution (v/v, 1:9) of O/ethanol, pH was adjusted to 8.0 with 1.0M NaOH, and the resulting mixture was continuously reversed in a water bath at 80 ℃ toThe time is 6.0 h; through centrifugal separation, washing with deionized water and ethanol, and drying at 60 ℃, the amidoxime functionalized hollow porous melamine resin microspheres are obtained, and are marked as MF-AO-HPS.
Using the same procedure as in step (3), except that MF-CHO-HP was replaced by MF-HP, another adsorbent without grafted PEA was obtained, denoted as MF-nPEA-AO-HPS.
SEM and TEM images of MF-HP are shown in FIG. 1; from the SEM image, we can see that the microspheres are monodisperse, they have a diameter of around 2.0 μm, the surface is porous, and from the TEM image, the microspheres are hollow.
Zeta potential and CP-MAS of each Compound by FT-IR, XPS and OEA13C NMR spectroscopy investigated grafting and chemical modification of MF-AO-HPS. MF-HP, MF-NH2FT-IR spectra of-HP, MF-CHO-HP, MF-CN-HP and MF-AO-HPS are shown in FIG. 2; at 2210cm in the MF-CN-HP spectrum-1The characteristic adsorption peak of C ≡ N shows that the DAMN modification is successful, and the disappearance of the adsorption peak in the MF-AO-HPS spectrogram is the same as NH2OH & HCl reaction.
From fig. 3, it can be seen that the Zeta potential changes after each reaction because the Zeta potential is shown to be different because the functional groups on the surface of the material are different after modification of different substances. This may reflect the success of each step of modification and the successful preparation of each material.
On the XPS spectrum of MF-AO-HPS, as shown in graph a in FIG. 4, it shows three strong peaks at 284.83, 399.03 and 535.88eV, corresponding to C1s, N1s and O1s core levels, respectively; panel b shows the C1s high resolution spectrum from which we can find that the C1s high resolution spectrum can be resolved into three peaks corresponding to C-C, C-H and C-N; and the graph C is an N1s high-resolution spectrogram of MF-AO-HPS, which can be split into three characteristic absorption peaks respectively attributed to N-O, C ═ N and N-H.
Fig. 5 shows the variation of the carbon and nitrogen atom content in each product. The test shows that the content of carbon atoms in MF-HP is less than that of nitrogen atoms, and the content of carbon atoms in PEA is greater than that of nitrogen atoms, so that MF-NH is compared with MF-HP2The carbon content in HP is relatively increased, andthe nitrogen content is relatively reduced. For the same reason, MF-CHO-HP and MF-CN-HP contain more carbon than nitrogen, and MF-AO-HPS contains more nitrogen than carbon.
FIG. 6 shows CP-MAS of MF-AO-HPS13C NMR spectrum chart containing four main signals of 48.12ppm, 105.80ppm, 162.72ppm and 219.75ppm, which correspond to-CH2Carbon absorption peaks of-NH-, -C ═ C-, C ═ NOH, and C ═ O; all the above results demonstrate the successful preparation of MF-AO-HPS; subsequently, the stability of MF-AO-HPS was determined by thermogravimetric analysis (TGA).
As shown in FIG. 7, a weight loss of 1.75% between 200 ℃ and 360 ℃ is observed in the MF-AO-HPS curve, due to the loss of the surface grafted amidoxime group, and a weight loss of 1.60% between 360 ℃ and 600 ℃ due to the loss of the grafted PEA. The small weight loss of MF-AO-HPS indicates that it has good stability.
Example 2:
(1) preparing silicon dioxide nano particles;
use of
Method for manufacturing silica nanoparticles: in a flask, 8.0g TEOS was added to 170mL ethanol, heated in a water bath to 30 ℃ and 9.0mL NH was added dropwise3··H2O and 9.0g H2A mixed solution of O; then reacting the formed mixed solution for 2.0h under magnetic stirring; after the reaction is finished, centrifuging and collecting a product, and washing the product for three times by using deionized water and ethanol respectively; drying to obtain silica nanoparticles with diameter of about 200 nm.
(2) Preparing hollow porous melamine resin;
1.0g of melamine was added to 2.0mL of a mixed solution of 37% formaldehyde and 25% glutaraldehyde (v/v, 2: 1) at 80 ℃ and then 2.0M Na was used2CO3Adjusting the pH value of the solution to 9.0, stirring at 1200rpm, and continuing to react for 4.0min after the solution is changed from milky white to clear; subsequently, 5.0 mL of a 10 wt% aqueous silica dispersion was added under stirring, and the reaction was continued for 10 min; the solution was then cooled to 3Dropwise adding 2M HCl at 0 ℃ to adjust the pH value to 5.0, continuously reacting for 10min, stopping stirring, and polymerizing for 3.0h under the condition of water bath at 30 ℃; finally, collecting a product through centrifugation, washing with deionized water and ethanol, and drying to obtain a powder sample; adding the obtained powder into 2% HF solution at room temperature for etching, centrifuging to collect the product, washing with deionized water and ethanol for three times respectively, centrifuging again to collect the product, and drying at 60 deg.C to obtain hollow porous melamine resin, which is marked as MF-HP;
(3) MF-AO-HPS can be obtained by the following method: first, 0.3g of MF-HP powder and 3.0g of PEA were dispersed in 40mL of ethanol in a flask, followed by sonication for 8.0 min; subsequently, the resulting mixture was reacted for 8.0h under magnetic stirring in a water bath at 30 ℃; then, the product is collected by centrifugation and washed with ethanol for three times to obtain the hollow porous melamine resin polymer microsphere with the surface grafted with amino, which is marked as MF-NH2-HP; secondly, 0.2g MF-NH2-HP, 8.0mL of 25% GA and 30mL of ethanol mixture were added to the flask, and then reacted for 8.0h under magnetic stirring in a 30 ℃ water bath; after the reaction is finished, washing the product with water for 3 times to remove excessive GA, then washing with ethanol for 2 times, and centrifugally collecting the hollow porous melamine resin polymer microspheres with aldehyde groups grafted on the surfaces, wherein the hollow porous melamine resin polymer microspheres are marked as MF-CHO-HP;
(4) 0.2g MF-CHO-HP and 0.4g DAMN were suspended in 40mL ethanol, sonicated for 8.0min, and reacted at 20 ℃ for 2.0h with magnetic stirring. Then collecting the product to obtain hollow porous melamine resin with the surface grafted with nitrile groups, and marking as MF-CN-HP; finally, 0.2g MF-CN-HP and 2.0g NH were added2OH HCl dispersed in 40mL H2In the O/ethanol mixed solution (v/v, 1:9), pH was adjusted to 8.5 using 1.0M NaOH, and the resulting mixture was allowed to react continuously for 4.0 hours in a water bath at 70 ℃; MF-AO-HPS is obtained by centrifugal separation, washing with distilled water and ethanol, and drying at 70 deg.C.
By MF-HP with DAMN and NH2The direct reaction of OH & HCl gives another adsorbent without grafted PEA, called MF-nPEA-AO-HPS.
Example 3:
(1) preparing silicon dioxide nano particles;
use of
Method for manufacturing silica nanoparticles: in a flask, 10g TEOS was added to 190mL ethanol, heated in a water bath to 40 ℃ and 11mL NH was added dropwise3·H2O and 10g H2And (3) mixed solution of O. The resulting mixed solution was then reacted for 4.0h with magnetic stirring. After the reaction was completed, the product was collected by centrifugation and washed three times with deionized water and ethanol, respectively. Drying to obtain silica nanoparticles with diameter of about 200 nm.
(2) Preparing hollow porous melamine resin;
2.0g of melamine was added to 4.0mL of a mixed solution of 37% formaldehyde and 25% glutaraldehyde (v/v, 2: 1) at 90 ℃ and then 2.0M Na was used2CO3Adjusting the pH value of the solution to 10.0, stirring the solution at 1600rpm, and continuing to react for 5.0min after the solution is changed from milky white to clear; subsequently, 15mL of a 10 wt% aqueous silica dispersion was added under stirring, and the reaction was continued for 30 min; then, cooling to 50 ℃, dropwise adding 2.0M HCl to adjust the pH value to 6.0, continuously reacting for 30min, stopping stirring, and polymerizing for 5.0h under the condition of 50 ℃ water bath; finally, collecting a product through centrifugation, washing with deionized water and ethanol, and drying to obtain a powder sample; adding the obtained powder into 2% HF solution at room temperature for etching, centrifuging to collect the product, washing with deionized water and ethanol for three times respectively, centrifuging again to collect the product, and drying at 60 deg.C to obtain hollow porous melamine resin, which is marked as MF-HP;
(3) first, 0.5g of MF-HP powder and 5.0g of PEA were dispersed in 60mL of ethanol in a flask, followed by sonication for 10 min. Subsequently, the resulting mixture was reacted for 16h under magnetic stirring in a water bath at 40 ℃; then, the product is collected by centrifugation and washed with ethanol for three times to obtain the hollow porous melamine resin polymer microsphere with the surface grafted with amino, which is marked as MF-NH2-HP; secondly, 0.4g of MF-NH2-HP, 12mL of a mixture of 25% GA and 50mL of ethanol were added to a 100mL single-necked flask, which was then placed under magnetic stirring in a water bath at 40 deg.CReacting for 16 h; after the reaction is finished, washing the product with water for three times to remove excessive GA, then washing with ethanol for two times, and centrifugally collecting the hollow porous melamine resin polymer microspheres with aldehyde groups grafted on the surfaces, wherein the hollow porous melamine resin polymer microspheres are marked as MF-CHO-HP;
(4) 0.6g MF-CHO-HP and 1.2g DAMN were suspended in 60mL ethanol, sonicated for 10min, and reacted at 30 ℃ for 4.0h with magnetic stirring. Then collecting the product to obtain hollow porous melamine resin with the surface grafted with nitrile groups, and marking as MF-CN-HP; finally, 0.6g of MF-CN-HP and 6.0g of NH were added2OH HCl dispersed in 60mL H2In O/ethanol (v/v, 1:9) solution, pH was adjusted to 9.0 using 1.0M NaOH, and the resulting mixture was allowed to react continuously for 8.0h in a water bath at 90 ℃; MF-AO-HPS is obtained by centrifugal separation, washing with deionized water and ethanol, and drying at 80 ℃.
By MF-HP with DAMN and NH2The direct reaction of OH & HCl gives another adsorbent without grafted PEA, called MF-nPEA-AO-HPS.
And (3) performance testing:
the pH value of the environment has great influence on the adsorption behavior of metal ions; the influence of MF-AO-HPS, MF-nPEA-AO-HPS and MF-HP on the adsorption capacity of U (VI) in the pH range of 3.0 to 9.0 was therefore investigated. As shown in FIG. 8, the adsorption capacities of MF-AO-HPS, MF-nPEA-AO-HPS and MF-HP all showed a gradual increase tendency with increasing pH at pH values of not higher than 7.0, the adsorption capacities thereof decreased with increasing pH values after pH values of higher than 7.0, and the adsorption capacities of MF-AO-HPS were higher than those of MF-nPEA-AO-HPS and MF-HP at any pH conditions.
The kinetics of adsorption of MF-AO-HPS for U (VI) are shown in FIG. 9. As can be seen, the adsorption capacity of MF-AO-HPS increased rapidly within the first 30min, reaching the maximum adsorption capacity within 60 min.
To investigate the maximum adsorption capacity of MF-AO-HPS, adsorption equilibrium experiments were performed at U (VI) concentrations in the range of 10-500mg/L, adsorption data were fitted using Langmuir and Freundlich models, and the effect of temperature on adsorption capacity was explored. As shown in fig. 10, the adsorption capacity increases with increasing temperature over the test temperature range.
The combination of interference ions and amidoxime groups has great influence on the adsorption capacity of MF-AO-HPS for adsorbing U (VI), so that VO is selected3-，Co2+，Ni+，Cu2+，Zn2+，Pb2+，Ca2+，Mg2+And Na+As competitive ions of U (VI), the adsorbent was studied in VO3-，Co2+，Ni+，Cu2+，Zn2+，Pb2+， Ca2+，Mg2+，Na+And adsorption behavior in the mixed solution of U (VI). As shown in FIG. 11, the MF-AO-HPS pair U (VI) still has the highest adsorption capacity in the presence of numerous interfering ions, much larger than VO3-，Co2+， Ni+，Cu2+，Zn2+，Pb2+，Ca2+，Mg2+And Na+Corresponding adsorption capacity.
Adsorption regenerability is an important index for evaluating stability of an adsorbent in a recycling process, so that the adsorption regenerability of MF-AO-HPS was tested by 7 consecutive adsorption-desorption cycle experiments. As shown in FIG. 12, the MF-AO-HPS still has higher adsorption capacity after 7 adsorption-desorption cycle experiments, which indicates that it has better adsorption regeneration performance and can maintain good adsorption capacity to U (VI) during the cycle use.
Description of the drawings: the above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; thus, while the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.
Claims (10)
1. By using CO2The method for preparing the amidoxime functionalized hollow porous polymer microspheres for the emulsion template is characterized by comprising the following steps of:
(1) preparing silicon dioxide nano particles;
(2) dispersing the silica nanoparticles obtained in the step (1) in deionized water to obtain silica aqueous dispersion; then, under a certain temperature condition, adding melamine into a mixed solution of a formaldehyde solution and a glutaraldehyde solution, adjusting the pH value of the mixed solution, stirring, and continuing to react for a period of time after the solution is changed from milky white to clear; after the reaction, adding the silicon dioxide aqueous dispersion under the stirring condition for reaction; cooling to a certain temperature after reaction, adjusting the pH value again, reacting, performing polymerization reaction under a water bath condition after reaction, finally, collecting a product by centrifugation, washing with deionized water and ethanol, and drying to obtain a powder sample; adding the powder sample into hydrofluoric acid solution for etching, centrifuging, collecting the product, washing with deionized water and ethanol, centrifuging again, collecting the product, and drying to obtain hollow porous melamine resin, which is recorded as MF-HP;
(3) dispersing the MF-HP and the polyethylene polyamine prepared in the step (2) in ethanol to obtain a mixed solution A, then carrying out ultrasonic treatment, and placing the mixed solution A under the condition of magnetic stirring in a water bath for reaction; centrifuging after reaction, washing the obtained product with ethanol, centrifuging again and collecting the product to obtain the hollow porous melamine resin polymer microsphere with the surface grafted with amino, and marking as MF-NH2-HP; then MF-NH2Adding HP and glutaraldehyde into ethanol to obtain a mixed solution B, and then placing the mixed solution B under the condition of magnetic stirring in a water bath for reaction; after the reaction is finished, washing the product with deionized water and ethanol respectively, and centrifuging to obtain hollow porous melamine resin polymer microspheres with aldehyde groups grafted on the surfaces, wherein the hollow porous melamine resin polymer microspheres are marked as MF-CHO-HP;
(4) suspending the MF-CHO-HP and the diaminomaleonitrile prepared in the step (3) in ethanol E to obtain a mixed solution C, then carrying out ultrasonic treatment, and placing the mixed solution C under the condition of magnetic stirring in a water bath for reaction; centrifuging after reaction to obtain hollow porous melamine resin with the surface grafted with nitrile groups, and marking as MF-CN-HP; finally, adding the ethanol F into deionized water to obtain a mixed solution of the ethanol and the water, adding the MF-CN-HP and the hydroxylamine hydrochloride, adjusting the pH value, and then placing the mixture under a water bath condition for reaction; and centrifuging after reaction, collecting a product, washing with deionized water and ethanol, and drying to obtain the amidoxime functionalized hollow porous melamine resin microsphere, which is recorded as MF-AO-HPS.
2. A method of using CO as claimed in claim 12The method for preparing the amidoxime functionalized hollow porous polymer microspheres as the emulsion template is characterized in that the certain temperature condition in the step (2) is 80-90 ℃; the dosage ratio of the melamine, the formaldehyde and the glutaraldehyde mixed solution to the silicon dioxide dispersion liquid is 1.0-2.0g, 2.0-4.0mL and 5.0-15 mL; the volume fraction of the formaldehyde solution is 37 percent, and the volume fraction of the glutaraldehyde solution is 25 percent; the concentration of the aqueous silica dispersion was 10 wt%.
3. A method of using CO as claimed in claim 12The method for preparing amidoxime functionalized hollow porous polymer microspheres for emulsion templates is characterized in that Na is used for pH adjustment in the step (2)2CO3Adjusting the pH value of the solution to 9.0-10.0; the Na is2CO3The concentration of the solution was 2.0M; the stirring condition is 1200-1600 rpm; the continuous reaction is carried out for 3.0-5.0 min; the time for adding the silicon dioxide aqueous dispersion to carry out reaction is 10-30 min.
4. A method of using CO as claimed in claim 12The method for preparing the amidoxime functionalized hollow porous polymer microspheres for the emulsion template is characterized in that in the step (2), the mixture is cooled to a certain temperature of 30-50 ℃; the operation of adjusting the pH again is as follows: dropwise adding HCl with the concentration of 2.0M to adjust the pH value to 5.0-6.0; the reaction time after the pH is adjusted again is 10-30 min; the temperature of the water bath is 30-50 ℃; the time of the polymerization reaction is 3.0 to 5.0 hours; the volume concentration of the hydrofluoric acid solution is 2%; the drying temperature is 60-80 ℃.
5. A method of using CO as claimed in claim 12Preparation of amidoximes for emulsion templateThe method for functionalizing the hollow porous polymer microspheres is characterized in that the dosage ratio of MF-HP, polyethylene polyamine and ethanol in the step (3) is 0.3-0.5mg:3.0-5.0 g: 40-60 mL.
6. A method of using CO as claimed in claim 12The method for preparing the amidoxime functionalized hollow porous polymer microspheres for the emulsion template is characterized in that the ultrasonic treatment time in the step (3) is 5.0-10 min; the temperature of the water bath of the mixed solution A is 30-40 ℃, and the reaction time is 8.0-16 h.
7. A method of using CO as claimed in claim 12The method for preparing amidoxime functionalized hollow porous polymer microspheres for emulsion templates is characterized in that the MF-NH in the step (3)2-the ratio of the amounts of HP, glutaraldehyde and ethanol is between 0.2 and 0.4 mg: 8.0-12 mL: 30-50 mL; the volume fraction of the glutaraldehyde is 25%; the temperature of the water bath of the mixed solution B is 20-30 ℃, and the reaction time is 8.0-16 h.
8. A method of using CO as claimed in claim 12The method for preparing the amidoxime functionalized hollow porous polymer microspheres for the emulsion template is characterized in that the dosage ratio of MF-CHO-HP, diaminomaleonitrile and ethanol E in the step (4) is 0.2-0.6mg:0.4-1.2 mg: 40-60 mL; the ultrasonic treatment time of the mixed solution C is 5.0-10min, the water bath temperature is 20-30 ℃, and the reaction time is 2.0-4.0 h.
9. A method of using CO as claimed in claim 12The method for preparing the amidoxime functionalized hollow porous polymer microspheres for the emulsion template is characterized in that the volume ratio of ethanol F to water in the step (4) is 9: 1; the dosage ratio of the mixed solution of MF-CN-HP, hydroxylamine hydrochloride, ethanol and water is 0.2-0.6mg: 2.0-6.0 g: 40-60 mL; the pH is adjusted to 8.0-9.0 by using 1.0M NaOH; after the pH value is adjusted, the mixture is placed under the water bath condition for reaction, the water bath temperature is 70-90 ℃, and the water bath reaction time is 4.0-8.0 h; said driedThe temperature is 60-80 deg.CoC。
10. The amidoxime functionalized hollow porous adsorbent prepared by the method according to any one of claims 1 to 9 is used for selective adsorption and separation of hexavalent uranium in solution.
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| PCT/CN2020/092492 WO2021093306A1 (en) | 2019-11-11 | 2020-05-27 | Method for preparing amidoxime functionalized hollow porous polymer microsphere by using co2 as emulsion template |
| GB2018087.3A GB2590792B (en) | 2019-11-11 | 2020-05-27 | Method for preparing amidoxime functionalized hollow porous polymer microspheres using CO2 as emulsion template |
| CH01488/20A CH717047B1 (en) | 2019-11-11 | 2020-05-27 | Process for preparing amidoxime-functionalized hollow porous polymeric microspheres using CO2 as the emulsion pattern. |
| JP2020565747A JP7207765B2 (en) | 2019-11-11 | 2020-05-27 | A Method for Preparing Amidoxime-Functionalized Hollow Porous Polymeric Microbeads as Emulsion Templates |
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| CN112642411B (en) * | 2020-12-17 | 2023-05-05 | 江苏大学 | Preparation method and application of porous/ion-rich channel microsphere adsorbent |
| CN112892497B (en) * | 2021-01-19 | 2023-03-21 | 江苏大学 | Preparation method and application of basin-covering type hollow porous polymer microspheres |
| CN113060750B (en) * | 2021-03-17 | 2022-04-08 | 电子科技大学 | Preparation method of mesoporous ionic compound for extracting uranium from seawater |
| CN114160103B (en) * | 2021-11-24 | 2023-09-22 | 江苏大学 | Preparation method of three-dimensional large Kong Xiean oximation ion gel adsorbent |
| CN114653348B (en) * | 2022-01-19 | 2023-10-10 | 江苏大学 | Method for preparing functional porous hydrogel based on liquid-gas droplet reactor |
| CN114570339B (en) * | 2022-01-28 | 2023-12-05 | 上海纳鸿微球科技有限公司 | Method for preparing salicylaldoxime/polydopamine hollow nano adsorbent by one-step method and uranium removal application thereof |
| CN114433036B (en) * | 2022-01-28 | 2024-04-16 | 深圳万知达技术转移中心有限公司 | Method for preparing amidoxime functionalized hollow polymer spheres based on solvent mixing-induced bubble template method and application of amidoxime functionalized hollow polymer spheres in uranium extraction |
| CN114643046B (en) * | 2022-02-14 | 2024-04-09 | 珠海维迈克建筑安装工程有限公司 | Preparation method of amidoxime microgel adsorbent and application thereof in rapid uranium extraction |
| CN114984924B (en) * | 2022-04-21 | 2022-11-01 | 哈尔滨工程大学 | Nano-pore structure uranium extraction from seawater adsorbing material and pore diameter regulation preparation method |
| CN114984919A (en) * | 2022-06-10 | 2022-09-02 | 浙江理工大学 | Double amidoxime group-based cellulose adsorbing material and preparation method thereof |
| CN115554988B (en) * | 2022-10-27 | 2023-12-22 | 昆明理工大学 | Organic chain modified zirconium-based MOF adsorbent and preparation method and application thereof |
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| JP2006026588A (en) * | 2004-07-20 | 2006-02-02 | Japan Atom Energy Res Inst | Method for recovering and removing useful or harmful metal dissolved in hot-spring water |
| JP2007284844A (en) * | 2006-04-20 | 2007-11-01 | Japan Atomic Energy Agency | Method for introducing amidoxime group to polymeric substrate in high density and product produced thereby |
| US20130168322A1 (en) * | 2010-09-14 | 2013-07-04 | Kaneka Corporation | Amidoxime-modified polyacrylonitrile porous body |
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| CN105817213B (en) * | 2016-05-23 | 2018-04-03 | 大连工业大学 | A kind of application of adsorbent based on hollow mesoporous silicon oxide and preparation method thereof and recovery gold |
| CN106902747B (en) * | 2017-03-29 | 2019-09-13 | 东华理工大学 | A kind of amidoxim mesoporous silicon dioxide micro-sphere adsorbent and preparation method thereof |
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| CN108160058B (en) * | 2018-01-15 | 2020-11-03 | 大连工业大学 | Magnetizable hollow mesoporous/microporous composite nano adsorbent, preparation method thereof and application of magnetizable hollow mesoporous/microporous composite nano adsorbent in adsorption of heavy metal ions |
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