CN115252571B - Porous aminated organic fluorine capsule and preparation method and application thereof - Google Patents
Porous aminated organic fluorine capsule and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a porous aminated organic fluorine capsule, which comprises a porous organic fluorine shell, wherein aminated phenolic resin is filled in the organic fluorine shell. The invention also discloses a preparation method of the porous aminated organic fluorine capsule. The invention also discloses application of the porous aminated organic fluorine capsule in adsorbing perfluorinated compounds, wherein the porous aminated organic fluorine capsule is mixed with perfluorinated compounds, and the porous aminated organic fluorine capsule is oscillated at a constant temperature of 24-26 ℃, and the mass concentration ratio of the porous aminated organic fluorine capsule material to the perfluorinated compounds is 5-100:1. The porous organic fluorine capsule material is synthesized based on common membrane materials of polyvinylidene fluoride, pore-forming agent polyvinylpyrrolidone and self-made aminated phenolic resin by a solvent substitution method, and the high-efficiency selective removal of the anionic perfluorinated compounds is successfully realized under the synergistic effect of an organic fluorine shell of the capsule and the internal aminated phenolic resin, and the raw materials are low in cost, easy to obtain and simple and convenient to prepare.
Description
Technical Field
The invention belongs to capsules and a preparation method and application thereof, in particular to a porous aminated organic fluorine capsule and a preparation method and application thereof.
Background
Perfluoro compounds (PFCs) are novel artificially synthesized fluorides with surfactant property, which take alkyl chains formed by fluorocarbon bonds as a framework, and the ion heads are connected with different functional groups, and the chemical formula is F (CF) 2 ) n -R. Since the first synthesis of 3M company at the end of 40 th centuryPFCs are widely used in various fields of human production and life due to their hydrophobic and lipophobic properties, high temperature resistance and strong oxidation resistance. The research shows that the PFCs are commonly existing in the global environment due to the use of a large amount and the strong stability thereof, and the concentration in surface water and underground water can reach up to 1 mg.L -1 . Of the 3000 PFCs that are put on the market, perfluorooctanoic acid (PFOA) is the most representative, and is not only produced in a large amount but also the final product of the conversion of various PFCs in the environment and organisms, and the detection frequency and concentration are extremely high. PFOA in the environment mainly enters the human body through food and drinking water, and has certain teratogenic and carcinogenic effects. In the last forty years, the PFOA content in human serum is continuously increased, and the highest concentration reaches 5 mug.L -1 。
To eliminate the adverse effects of such contaminants on the environment and organisms, regulatory guidelines have been issued to limit sales and use of PFOA, which is also listed in the persistent organic contaminant priority control list, the healthy limiting concentration of PFOA in drinking water being 70 ng.L -1 . PFASs removal techniques have been intensively studied for both environmental and human health.
According to related researches, the advanced reduction technology based on water and electrons and the advanced oxidation technology based on sulfate radical can effectively treat the high-concentration PFOA polluted wastewater, but has poor effect of removing trace PFOA in the water body of the actual environment. Therefore, if the trace PFOA in the water body is to be subjected to innocent treatment, the trace PFOA is firstly subjected to selective adsorption concentration.
At present, the traditional adsorption technology (activated carbon, ion exchange resin, mineral material) and the like existing in the market have low removal efficiency and poor anti-interference performance. Therefore, researchers develop a series of new materials for selectively adsorbing PFOA, such as covalent organic fluorine framework materials (COFs), organic fluorine modified clay minerals and the like, but the problems of high cost, poor anti-interference performance, easiness in secondary pollution and the like still exist.
Therefore, there is a need to develop an adsorbent material that is low-cost, easy to separate and capable of selectively adsorbing trace amounts of PFOA in a body of water in a real environment.
Disclosure of Invention
The invention aims to: in order to overcome the defects in the prior art, the invention aims to provide a porous aminated organic fluorine capsule, and another aim of the invention is to provide a preparation method of the porous aminated organic fluorine capsule, and further aim of the invention is to provide an application of the porous aminated organic fluorine capsule in adsorbing perfluorinated compounds.
The technical scheme is as follows: the porous aminated organic fluorine capsule comprises a porous organic fluorine shell, wherein aminated phenolic resin is filled in the organic fluorine shell.
Further, the pore diameter of the porous organofluorine shell is 28.6-330.5 nm, and the pore diameter decreases with increasing content of aminated phenolic resin in the capsule.
Further, the diameter of the porous aminated organic fluorine capsule is 1.5-1.8 mm.
The preparation method of the porous aminated organic fluorine capsule comprises the following steps:
s1, dissolving ethylenediamine, formaldehyde and resorcinol in an alcohol-water mixed solution, stirring at 25-30 ℃, synthesizing aminated phenolic resin through polymerization reaction, washing with ultrapure water, centrifuging, drying at 90-100 ℃ for 12-16 hours, and grinding into aminated phenolic resin powder;
s2, mixing polyvinylidene fluoride, polyvinylpyrrolidone and aminated phenolic resin powder, dispersing in an N, N-dimethylformamide solvent, continuously stirring for 2-4 hours at 50-60 ℃ to ensure that the mixture is uniformly dispersed and air bubbles are removed, and obtaining a gel-state mixture;
s3, using a mixed solution of water and isopropanol as a solvent exchange solution, and dripping the gel-state mixture obtained in the S2 into the solvent exchange solution by using a syringe under the condition of stirring at the temperature of 25-30 ℃ to obtain a half-cooked capsule;
s4, dispersing the semi-cooked capsule obtained in the step S3 in pure water, stirring, and then carrying out vacuum drying at 90-100 ℃ to obtain the porous aminated organic fluorine capsule.
Further, in S1, the mass ratio of ethylenediamine, formaldehyde and resorcinol is 1-3:1-2. In the alcohol-water mixed solution, the volume ratio of the ethanol to the water is 2:5.
Further, in S2, the mass concentration ratio of the polyvinylidene fluoride to the polyvinylpyrrolidone to the aminated phenolic resin powder is 12:2:4-12. The weight average molecular weight of polyvinylidene fluoride was 170000 ～ 190000. The weight average molecular weight of polyvinylpyrrolidone was 1200000 ～ 1400000.
Further, in S3, the volume ratio of isopropyl alcohol to water in the mixed solution of water and isopropyl alcohol is 30%.
The porous aminated organic fluorine capsule is used for adsorbing the perfluorinated compound, the porous aminated organic fluorine capsule and the perfluorinated compound are mixed, and the mixture is oscillated at the constant temperature of 24-26 ℃, wherein the mass concentration ratio of the porous aminated organic fluorine capsule material to the perfluorinated compound is 5-100:1.
Further, the pH of the porous aminated organic fluorine capsule after being mixed with the perfluorinated compound is adjusted to be 2-9.25, and the adsorption rate of the perfluorinated compound is more than 95%.
Adsorption principle: the polyvinylidene fluoride with a structure similar to that of the perfluorinated compound is used as a raw material, so that the nonpolar and lipophobic properties of the capsule shell are enhanced, the interference of strong polar inorganic matters such as salt ions and lipophilic organic matters such as humus is effectively eliminated, and the selectivity of the perfluorinated compound is further improved. The aminated phenolic resin can adsorb the PFASs in the solution through electrostatic attraction, and the porous organic fluorine shell protects the adsorption of the aminated phenolic resin to the PFASs from being disturbed.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable characteristics:
1. based on common membrane materials of polyvinylidene fluoride, pore-forming agent polyvinylpyrrolidone and self-made aminated phenolic resin, synthesizing a porous organic fluorine capsule material by a solvent replacement method, and successfully realizing the efficient selective removal of anionic perfluorinated compounds under the synergistic effect of an organic fluorine shell of the capsule and the internal aminated phenolic resin, wherein the raw materials are cheap and easily available, and the preparation process is simple and convenient to operate;
2. the porous aminated organic fluorine capsule material realizes high-efficiency selective adsorption of the perfluorinated compounds in a wide pH range, has good adaptability to strong acid and strong alkali environments, can still reach more than 95% of the perfluorinated compounds even under the condition of strong alkalinity, and can be used in extreme environments;
3. the porous aminated organic fluorine capsule material not only maintains the particle form of the traditional commercial activated carbon and ion exchange resin, but also does not reduce the residence time of the capsule in water treatment, and simultaneously has large particles and is easy to recycle;
4. the capsule has good reusability, the adsorption capacity of the capsule after adsorbing the PFOA can be recovered through eluting the methanol solution, the adsorption quantity of the capsule to the PFOA is almost unchanged after repeating for 5 times, and the capsule has good economic applicability and bright prospect.
Drawings
FIG. 1 is a synthetic route diagram of the present invention;
FIG. 2 is a scanning electron microscope and a size distribution chart of the invention, wherein a is an electron microscope of an aminated phenol resin under a 1 μm scale, b is an electron microscope of an aminated phenol resin under a 200nm scale, c is a size distribution chart of an aminated phenol resin, d is an electron microscope of FC under a 100 μm scale, e is an electron microscope of FC under a 2 μm scale, f is a surface channel distribution chart of FC, g is an electron microscope of AFC-1 under a 100 μm scale, h is an electron microscope of AFC-1 under a 200nm scale, i is a surface channel distribution chart of AFC-1, j is an electron microscope of AFC-2 under a 100 μm scale, k is an electron microscope of AFC-2 under a 200nm scale, l is a surface channel distribution chart of AFC-2, m is an electron microscope of AFC-3 under a 100 μm scale, n is an electron microscope of AFC-3 under a 200nm scale, o is a surface channel distribution chart of AFC-3;
FIG. 3 is a graph of the specific surface area profile of the porous aminated organic fluorine capsule material of the present invention;
FIG. 4 is a schematic infrared spectrum of a porous aminated organic fluorine capsule material of the present invention;
FIG. 5 is a schematic representation of zeta potential of the porous aminated organic fluorine capsule material of the present invention;
FIG. 6 is a graph of the adsorption heat of the porous aminated organic fluorine capsule material of the present invention on PFOA, wherein a is the graph of ANP on PFOA, and b is the graph of FC, AFC-1, AFC-2, AFC-3, AFC-4, AFC-5 on PFOA;
FIG. 7 is a graph comparing PFOA adsorption effects of different adsorbents of the present invention;
FIG. 8 is a graph of adsorption kinetics of the porous aminated organic fluorine capsule material of the present invention for various perfluorinated compounds;
FIG. 9 is a graph showing the effect of pH on PFOA adsorption by porous aminated organofluorine capsule materials in accordance with the present invention;
FIG. 10 is a graph showing the effect of coexisting substances in different environments on PFOA adsorption by a porous aminated organic fluorine capsule material, wherein a is a graph showing the effect of PFOA adsorption by AFC-2, and b is a graph showing the effect of PFOA adsorption by ANP;
FIG. 11 is a cyclic regeneration diagram of a porous aminated organic fluorine capsule material of the present invention.
Detailed Description
In the following examples, the weight average molecular weight of polyvinylidene fluoride was 170000 ～ 190000. The weight average molecular weight of polyvinylpyrrolidone was 1200000 ～ 1400000.
Example 1
As shown in fig. 1, a preparation method of the porous aminated organic fluorine capsule material comprises the following steps:
s1, dissolving ethylenediamine, formaldehyde and resorcinol in a mass ratio of 1:3:2 into an alcohol-water mixed solution, stirring the mixture for 24 hours at 30 ℃ with ethanol and water in a volume ratio of 2:5, synthesizing aminated phenolic resin through polymerization reaction, washing the mixture with ultrapure water for 5 times, centrifuging, drying the precipitate obtained after washing in a blast drying oven at 100 ℃ for 12 hours, and grinding the precipitate into aminated phenolic resin powder (ANP);
s2, mixing polyvinylidene fluoride (PVDF), polyvinylpyrrolidone (PVP) and aminated phenolic resin powder (ANP), wherein the mass concentration ratio of the polyvinylidene fluoride to the polyvinylpyrrolidone to the aminated phenolic resin powder is 12:2:4, dispersing the mixture in N, N-dimethylformamide solvent (DMF), and continuously stirring the mixture at 60 ℃ for 2 hours to obtain a gel-state mixture;
s3, using a mixed solution of water and isopropanol as a solvent exchange solution, wherein the volume ratio of the isopropanol to the water is 30%, dripping the gel-state mixture obtained in the S2 into the solvent exchange solution by using a syringe while stirring at 25 ℃, and continuously stirring for 2 hours to obtain a half-cooked capsule;
s4, dispersing the semi-cooked capsules obtained in the step S3 in pure water, stirring for 24 hours, and then vacuum drying in a vacuum drying oven at 100 ℃ for 12 hours to obtain porous aminated organic fluorine capsules which are named as AFC-1.
Example 2
A method for preparing a porous aminated organic fluorine capsule material, comprising the following steps:
s1, dissolving ethylenediamine, formaldehyde and resorcinol in a mass ratio of 1:3:2 into an alcohol-water mixed solution, stirring the mixture for 24 hours at 30 ℃ with the volume ratio of ethanol to water, synthesizing aminated phenolic resin through polymerization reaction, washing the aminated phenolic resin with ultrapure water for 5 times, centrifuging, drying the precipitate obtained after washing in a blast drying oven at 100 ℃ for 12 hours, and grinding the precipitate into aminated phenolic resin powder;
s2, mixing PVDF, PVP and ANP, wherein the mass concentration ratio of polyvinylidene fluoride to polyvinylpyrrolidone to aminated phenolic resin powder is 12:2:6, dispersing in DMF, and continuously stirring at 60 ℃ for 2 hours to obtain a gel-state mixture;
s3, using a mixed solution of water and isopropanol as a solvent exchange solution, wherein the volume ratio of the isopropanol to the water is 30%, dripping the gel-state mixture obtained in the S2 into the solvent exchange solution by using a syringe while stirring at 25 ℃, and continuously stirring for 2 hours to obtain a half-cooked capsule;
s4, dispersing the semi-cooked capsules obtained in the step S3 in pure water, stirring for 24 hours, and then vacuum drying in a vacuum drying oven at 100 ℃ for 12 hours to obtain porous aminated organic fluorine capsules which are named as AFC-2.
Example 3
A method for preparing a porous aminated organic fluorine capsule material, comprising the following steps:
s1, dissolving ethylenediamine, formaldehyde and resorcinol in a mass ratio of 1:3:2 into an alcohol-water mixed solution, stirring the mixture for 24 hours at 30 ℃ with the volume ratio of ethanol to water, synthesizing aminated phenolic resin through polymerization reaction, washing the aminated phenolic resin with ultrapure water for 5 times, centrifuging, drying the precipitate obtained after washing in a blast drying oven at 100 ℃ for 12 hours, and grinding the precipitate into aminated phenolic resin powder;
s2, mixing PVDF, PVP and ANP, wherein the mass concentration ratio of polyvinylidene fluoride to polyvinylpyrrolidone to aminated phenolic resin powder is 12:2:8, dispersing in DMF, and continuously stirring at 60 ℃ for 2 hours to obtain a gel-state mixture;
s3, using a mixed solution of water and isopropanol as a solvent exchange solution, wherein the volume ratio of the isopropanol to the water is 30%, dripping the gel-state mixture obtained in the S2 into the solvent exchange solution by using a syringe while stirring at 25 ℃, and continuously stirring for 2 hours to obtain a half-cooked capsule;
s4, dispersing the semi-cooked capsules obtained in the step S3 in pure water, stirring for 24 hours, and then vacuum drying in a vacuum drying oven at 100 ℃ for 12 hours to obtain porous aminated organic fluorine capsules which are named as AFC-3.
Example 4
A method for preparing a porous aminated organic fluorine capsule material, comprising the following steps:
s1, dissolving ethylenediamine, formaldehyde and resorcinol in a mass ratio of 1:3:2 into an alcohol-water mixed solution, stirring the mixture for 24 hours at 30 ℃ with the volume ratio of ethanol to water, synthesizing aminated phenolic resin through polymerization reaction, washing the aminated phenolic resin with ultrapure water for 5 times, centrifuging, drying the precipitate obtained after washing in a blast drying oven at 100 ℃ for 12 hours, and grinding the precipitate into aminated phenolic resin powder;
s2, mixing PVDF, PVP and ANP, wherein the mass concentration ratio of polyvinylidene fluoride to polyvinylpyrrolidone to aminated phenolic resin powder is 12:2:10, dispersing in DMF, and continuously stirring at 60 ℃ for 2 hours to obtain a gel-state mixture;
s3, using a mixed solution of water and isopropanol as a solvent exchange solution, wherein the volume ratio of the isopropanol to the water is 30%, dripping the gel-state mixture obtained in the S2 into the solvent exchange solution by using a syringe while stirring at 25 ℃, and continuously stirring for 2 hours to obtain a half-cooked capsule;
s4, dispersing the semi-cooked capsules obtained in the step S3 in pure water, stirring for 24 hours, and then vacuum drying in a vacuum drying oven at 100 ℃ for 12 hours to obtain porous aminated organic fluorine capsules which are named as AFC-4.
Example 5
A method for preparing a porous aminated organic fluorine capsule material, comprising the following steps:
s1, dissolving ethylenediamine, formaldehyde and resorcinol in a mass ratio of 1:3:2 into an alcohol-water mixed solution, stirring the mixture for 24 hours at 30 ℃ with the volume ratio of ethanol to water, synthesizing aminated phenolic resin through polymerization reaction, washing the aminated phenolic resin with ultrapure water for 5 times, centrifuging, drying the precipitate obtained after washing in a blast drying oven at 100 ℃ for 12 hours, and grinding the precipitate into aminated phenolic resin powder;
s2, mixing PVDF, PVP and ANP, wherein the mass concentration ratio of polyvinylidene fluoride to polyvinylpyrrolidone to aminated phenolic resin powder is 12:2:12, dispersing in DMF, and continuously stirring at 60 ℃ for 2 hours to obtain a gel-state mixture;
s3, using a mixed solution of water and isopropanol as a solvent exchange solution, wherein the volume ratio of the isopropanol to the water is 30%, dripping the gel-state mixture obtained in the S2 into the solvent exchange solution by using a syringe while stirring at 25 ℃, and continuously stirring for 2 hours to obtain a half-cooked capsule;
s4, dispersing the semi-cooked capsules obtained in the step S3 in pure water, stirring for 24 hours, and then vacuum drying in a vacuum drying oven at 100 ℃ for 12 hours to obtain porous aminated organic fluorine capsules which are named as AFC-5.
Comparative example
A method for preparing a porous aminated organic fluorine capsule material, comprising the following steps:
s1, mixing PVDF, PVP and ANP, wherein the mass concentration ratio of polyvinylidene fluoride to polyvinylpyrrolidone is 12:2, dispersing in DMF, and continuously stirring at 60 ℃ for 2 hours to obtain a gel-state mixture;
s2, using a mixed solution of water and isopropanol as a solvent exchange solution, wherein the volume ratio of the isopropanol to the water is 30%, dripping the gel-state mixture obtained in the step S1 into the solvent exchange solution by using a syringe while stirring at 25 ℃, and continuously stirring for 2 hours to obtain a half-cooked capsule;
and S3, dispersing the semi-cooked capsules obtained in the step S2 in pure water, stirring for 24 hours, and then vacuum drying in a vacuum drying oven at 100 ℃ for 12 hours to obtain porous aminated organic fluorine capsules, which are named as FC.
Test 1
The ANP obtained in S1 in examples 1 to 5 was adhered to a scanning electron microscope sample stage with a conductive adhesive, and taken in a scanning electron microscope, as shown in fig. 2, to make a conclusion: ANP is uniform microsphere with average diameter of 225.3nm, FC without ANP is white sphere with diameter of 1.8-2 mm, and AFC-1-AFC-5 is yellow brown porous sphere with diameter of 1.5-1.8 mm. The FC surface contained channels with an average pore size of 5.4. Mu.m. The surface of AFC-1-AFC-4 also has abundant and uniform micropores, the pore diameter range is 28.6-330.5 nm, the pore diameter is reduced along with the increase of the ANP content in the capsule, and no void is observed on the surface of ACF-5.
Test 2
The porous aminated organofluorine capsules prepared in examples 1 to 5 were weighed out to have the same mass, and were prepared in N 2 The specific surface areas of different samples are tested by selecting a solution control mode on the adsorption and desorption instrument, and the test results are shown in figure 3. It can be concluded that: the specific surface area of ANP is 178.43m 2 g -1 The specific surface area of the FC was 98.89m 2 g -1 Specific surface areas of AFC-1, AFC-2, AFC-3, AFC-4 and AFC-5 were 132.96, 160.50, 155.22, 144.63 and 128.88m, respectively 2 g -1 The specific surface area showed a tendency to increase and decrease with increasing ANP content in the capsules, with AFC-2 having the largest specific surface area.
Test 3
Powder ANP, single particle FC and AFC were selected and the infrared signal of the selected samples were tested directly on a solid sample stage using the multiple Attenuated Total Reflection (ATR) mode, the data shown in fig. 4.
From this it can be concluded that: 2853.4 and 2925.6cm -1 Methylene (-CH) 2 The signal of (-) stretching vibration comes from the ANP where the different porous aminated organofluorine capsules show a stronger signal and as the ANP content increases, the gradual increase of the signal indicates a gradual increase of the ANP content in the capsules. 1604.3cm -1 Where the flexural vibration signal is the N-H bond in the amino group, where the stronger signal of ANP indicates that it contains rich amino groups, where the signal of different porous aminated organofluorine capsules increases with increasing ANP content, indicating that the amino content of the capsules is increasing.
Test 4
The porous aminated organic fluorine capsule is characterized by zeta potential meter, which comprises the following specific steps:
(1) The respective arrangements contain 1 g.L -1 FC (obtained in comparative example) and ANP solutions (obtained in example 1), the pH of the reaction solution was adjusted to 2 to 11 with NaOH of different concentrations;
(2) The zeta potential of the solution obtained in step (1) was measured by means of a zeta potential meter.
From this, it can be concluded that: the isoelectric points of ANP and FC are 9.25 and 6.88, respectively, which means that ANP attracts anionic perfluorinated compounds by electrostatic action over a wide pH range (ph=2 to 9.25).
Test 5
The adsorption thermodynamics of the porous aminated organic fluorine capsule on PFOA is examined, and the method comprises the following steps:
(1) 6 groups of initial concentrations of 10 to 200 mg.L are prepared -1 And 1 group of initial concentration of 10 to 900mgL -1 The PFOA solution of (2) was adjusted to pH 6 with NaOH of different concentrations, 5mgFC, AFC-1, AFC-2, AFC-3, AFC-4, AFC-5 and ANP were added respectively, and after sealing, they were oscillated by a constant temperature oscillator at a reaction temperature of 25.+ -. 1 ℃ and after 1 hour, two supernatants were taken out respectively as parallel samples to determine the PFOA concentration.
(2) Adsorption isotherms for PFOA were fitted using the langmuir model, model Q e ＝(K L ×Q max ×C e )/(1+K L ×C e ) The maximum adsorption amounts of PFOA on ANP, FC and AFC-1 to AFC-5 were 0.64837, 0.00031, 0.01038, 0.04559, 0.04013, 0.03322, 0.02278mgmg, respectively -1 The specific results are shown in FIG. 7.
From this it can be concluded that: the adsorption capacity of ANP to PFOA is extremely strong, and capsules without amination cannot adsorb PFOA; the adsorption effect of capsules with different raw material ratios on PFOA is different, and the general rule is that the adsorption efficiency of the capsules on PFOA is increased and then decreased with the increase of the ANP content. Of these, AFC-2 has the best effect of adsorbing PFOA.
Test 6
The PFOA adsorption of the porous aminated organic fluorine capsule AFC-2 with the strongest adsorption capacity and other adsorption materials is examined, and the specific steps are as follows:
(1) Configuration contains 1. Mu.gL -1 The pH of the reaction solution is regulated to 6 by NaOH with different concentrations;
(2) 5mg of AFC-2, FC, ANP and powdered activated carbon are respectively added into the solution obtained in the step (1), and the mixture is sealed and then oscillated by a constant-temperature oscillation box, wherein the reaction temperature is controlled to be 25+/-1 ℃ and the reaction time is 5 hours. Sampling time was set to 0, 0.1, 0.3, 0.6, 1, 5h, respectively. Two supernatants were taken at each time point as parallel samples to determine the PFOA adsorption rate, as shown in FIG. 7.
From this it can be concluded that: the powdered activated carbon and the FC hardly adsorb PFOA, the AFC-2 and the ANP have better adsorption effect on PFOA, and 1 mu gL can be realized in the first 1 hour -1 The concentration of PFOA is reduced to 70ngL -1 The following is given.
Test 7
The adsorption kinetics diagram of the porous aminated organic fluorine capsule to different perfluorinated compounds is examined, and the specific steps are as follows:
(1) The respective configuration contains 1. Mu.gL -1 5mL of trifluoroacetic acid (TFA), perfluorobutyric acid (PFBA), perfluorohexanoic acid (PFHxA), PFOA, perfluorooctanesulfonic acid (PFOS), hexafluoropropylene oxide trimer acid (HFPO-TA) and perfluorosuberic acid (PFdica) solution, and adjusting the pH of the reaction solution to 6 with NaOH of different concentrations;
(2) 5mg of AFC-2 is added into the solution obtained in the step (1), the solution is sealed and then oscillated by a constant temperature oscillation box, the reaction temperature is controlled to be 25+/-1 ℃, and two supernatants are taken out as parallel samples after 1 hour to measure the adsorption efficiency.
From this it can be concluded that: the porous aminated organic fluorine capsule has different adsorption effects on different perfluorinated compounds, has the best adsorption effect on PFOA, PFOS, HFPO-TA, and has the adsorption rate of more than 98 percent; the adsorption effect on TFA and PFdiCA is general.
Test 8
The influence of pH on the adsorption of perfluorinated compounds by porous aminated organic fluorine capsules is examined, and the method comprises the following specific steps:
(1) Configuration contains 1. Mu.gL -1 PFOA solution 5mL of the reaction solution was adjusted with NaOH of different concentrationsThe pH is 2, 4, 6, 8 and 10;
(2) 5mg of AFC-2 and ANP are respectively added into the solution obtained in the step (1), the solution is sealed and then oscillated by a constant temperature oscillation box, the reaction temperature is controlled to be 25+/-1 ℃, and two supernatants are respectively taken out after 1 hour to be used as parallel samples for measuring the adsorption efficiency.
From this it can be concluded that: when pH <8, pH has little effect on the process of AFC-2 and ANP adsorbing PFOA, whereas when pH >8, pH has a larger effect on the process of ANP adsorbing PFOA and a smaller effect on the process of AFC-2 adsorbing PFOA.
Test 9
The environment coexisting substances humic acid (SRHA), fulvic acid (SRFA)), small molecule acid (oxalic acid (OA), benzoic Acid (BA)) and salt ion (sodium chloride (NaCl), calcium chloride (CaCl) 2 ) The porous aminated organic fluorine capsule is used for adsorbing the perfluorinated compounds, and the specific steps are as follows:
(1) The respective configuration contains 1. Mu.gL -1 PFOA and environmentally coexisting materials of different concentrations (5 mgL -1 SRHA、SRFA，5mgL -1 NaCl、CaCl 2 10mMOA, BA) 5mL, adjusting the pH of the reaction solution to 6 with NaOH of different concentrations;
(2) 5mg of AFC-2 and ANP are respectively added into the solution obtained in the step (1), the solution is sealed and then oscillated by a constant temperature oscillation box, the reaction temperature is controlled to be 25+/-1 ℃, and two supernatants are respectively taken out after 1 hour and 5 hours to be used as parallel samples for measuring the adsorption efficiency. )
From this it can be concluded that: humus (SRHA, SRFA), small molecule acid (OA, BA) and salt ion (NaCl, caCl) 2 ) Has larger influence on the process of absorbing PFOA by ANP and smaller influence on the process of absorbing PFOA by AFC-2.
Test 10
The cyclic regeneration capability of the porous aminated organic fluorine capsule is examined, and the specific steps are as follows:
(1) The porous aminated organic fluorine capsule with saturated adsorption is placed in 5mL of methanol, and is sealed and then oscillated by a constant-temperature oscillation box, and the reaction temperature is controlled at 25+/-1 ℃. Two supernatants were taken after 10 hours as parallel samples to determine desorption efficiency.
(2) Taking out the desorbed porous aminated organic fluorine capsule, cleaning, drying and re-adsorbing 1 MugL -1 PFOA, repeat the above-mentioned desorption process 5 times, evaluate the cyclic regeneration efficiency of the capsule material comprehensively.
From this it can be concluded that: the porous aminated organic fluorine capsule has strong cyclic regeneration capability, and the adsorption capability to PFOA is almost unchanged after 5 times of adsorption-desorption.
Example 6
A method for preparing a porous aminated organic fluorine capsule material, comprising the following steps:
s1, dissolving ethylenediamine, formaldehyde and resorcinol in a mass ratio of 1:1:1 into an alcohol-water mixed solution, stirring the mixture for 24 hours at a temperature of 25-30 ℃ with ethanol and water in a volume ratio of 2:5, synthesizing aminated phenolic resin through polymerization reaction, washing the mixture with ultrapure water for 5 times, centrifuging, drying the precipitate obtained after washing in a blast drying oven at a temperature of 90 ℃ for 12 hours, and grinding the precipitate into aminated phenolic resin powder;
s2, mixing PVDF, PVP and ANP, dispersing in DMF, and continuously stirring at 50 ℃ for 2 hours to obtain a gel-state mixture;
s3, using a mixed solution of water and isopropanol as a solvent exchange solution, wherein the volume ratio of the isopropanol to the water is 30%, dripping the gel-state mixture obtained in the S2 into the solvent exchange solution by using a syringe while stirring at 25 ℃, and continuously stirring for 2 hours to obtain a half-cooked capsule;
and S4, dispersing the semi-cooked capsules obtained in the step S3 in pure water, stirring for 24 hours, and then vacuum drying in a vacuum drying oven at 90 ℃ for 12 hours to obtain the porous aminated organic fluorine capsules.
Example 7
A method for preparing a porous aminated organic fluorine capsule material, comprising the following steps:
s1, dissolving ethylenediamine, formaldehyde and resorcinol in a mass ratio of 3:3:2 into an alcohol-water mixed solution, stirring the mixture for 24 hours at a temperature of 25-30 ℃ with ethanol and water in a volume ratio of 2:5, synthesizing aminated phenolic resin through polymerization reaction, washing the mixture with ultrapure water for 5 times, centrifuging, drying the precipitate obtained after washing in a blast drying oven at a temperature of 100 ℃ for 16 hours, and grinding the precipitate into aminated phenolic resin powder;
s2, mixing PVDF, PVP and ANP, dispersing in DMF, and continuously stirring at 60 ℃ for 4 hours to obtain a gel state mixture;
s3, using a mixed solution of water and isopropanol as a solvent exchange solution, wherein the volume ratio of the isopropanol to the water is 30%, dripping the gel-state mixture obtained in the S2 into the solvent exchange solution by using a syringe while stirring at 30 ℃, and continuously stirring for 2 hours to obtain a half-cooked capsule;
and S4, dispersing the semi-cooked capsules obtained in the step S3 in pure water, stirring for 24 hours, and then vacuum drying in a vacuum drying oven at 100 ℃ for 12 hours to obtain the porous aminated organic fluorine capsules.
Example 8
A method for preparing a porous aminated organic fluorine capsule material, comprising the following steps:
s1, dissolving ethylenediamine, formaldehyde and resorcinol in a mass ratio of 2:2:1 into an alcohol-water mixed solution, stirring the mixture for 24 hours at a temperature of 25-30 ℃ with ethanol and water in a volume ratio of 2:5, synthesizing aminated phenolic resin through polymerization reaction, washing the mixture with ultrapure water for 5 times, centrifuging, drying the precipitate obtained after washing in a blast drying oven at a temperature of 95 ℃ for 14 hours, and grinding the precipitate into aminated phenolic resin powder (ANP);
s2, mixing PVDF, PVP and ANP, dispersing in DMF, and continuously stirring at 55 ℃ for 3 hours to obtain a gel state mixture;
s3, using a mixed solution of water and isopropanol as a solvent exchange solution, wherein the volume ratio of the isopropanol to the water is 30%, dripping the gel-state mixture obtained in the S2 into the solvent exchange solution by using a syringe while stirring at 27 ℃, and continuously stirring for 2 hours to obtain a half-cooked capsule;
and S4, dispersing the semi-cooked capsules obtained in the step S3 in pure water, stirring for 24 hours, and then vacuum drying in a vacuum drying oven at 95 ℃ for 12 hours to obtain the porous aminated organic fluorine capsules.
Claims (9)
1. A porous aminated organic fluorine capsule characterized in that: the porous organic fluorine shell is filled with aminated phenolic resin;
the preparation method of the porous aminated organic fluorine capsule comprises the following steps:
s1, dissolving ethylenediamine, formaldehyde and resorcinol in an alcohol-water mixed solution, stirring at 25-30 ℃, synthesizing aminated phenolic resin through polymerization, washing with ultrapure water, centrifuging, drying at 90-100 ℃ for 12-16 hours, and grinding into aminated phenolic resin powder;
s2, mixing polyvinylidene fluoride, polyvinylpyrrolidone and aminated phenolic resin powder, dispersing in an N, N-dimethylformamide solvent, and continuously stirring for 2-4 hours at 50-60 ℃ to obtain a gel-state mixture;
s3, using a mixed solution of water and isopropanol as a solvent exchange solution, and dripping the gel-state mixture obtained in the step S2 into the solvent exchange solution at the temperature of 25-30 ℃ while stirring to obtain a semi-cooked capsule;
and S4, dispersing the semi-finished capsules obtained in the step S3 in pure water, stirring, and then carrying out vacuum drying at 90-100 ℃ to obtain the porous aminated organic fluorine capsules.
2. A porous aminated organic fluorine capsule according to claim 1, characterized in that: the pore diameter of the porous organic fluorine shell is 28.6-330.5-nm, and the pore diameter is reduced along with the increase of the content of the aminated phenolic resin in the capsule.
3. A porous aminated organic fluorine capsule according to claim 1, characterized in that: the diameter of the porous aminated organic fluorine capsule is 1.5-1.8 mm.
4. A porous aminated organic fluorine capsule according to claim 1, characterized in that: in the S1, the mass ratio of the ethylenediamine to the formaldehyde to the resorcinol is 1-3:1-2.
5. A porous aminated organic fluorine capsule according to claim 1, characterized in that: in the S2, the mass concentration ratio of the polyvinylidene fluoride to the polyvinylpyrrolidone to the aminated phenolic resin powder is 12:2:4-12.
6. A porous aminated organic fluorine capsule according to claim 1, characterized in that: in the step S2, the weight average molecular weight of the polyvinylidene fluoride is 170000-190000.
7. A porous aminated organic fluorine capsule according to claim 1, characterized in that: in the step S2, the weight average molecular weight of polyvinylpyrrolidone is 1200000 to 1400000.
8. The use of a porous aminated organic fluorine capsule according to any one of claims 1 to 3 for adsorbing perfluorinated compounds, characterized in that: mixing the porous aminated organic fluorine capsule with the perfluorinated compound, and oscillating at a constant temperature of 24-26 ℃, wherein the mass concentration ratio of the porous aminated organic fluorine capsule material to the perfluorinated compound is 5-100:1.
9. The use of a porous aminated organic fluorine capsule according to claim 8 for adsorbing perfluorinated compounds, characterized in that: the pH value of the porous aminated organic fluorine capsule and the perfluorinated compound after being mixed is adjusted to 2-9.25, and the adsorption rate of the perfluorinated compound is more than 95%.
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| US11660574B2 (en) * | 2020-05-28 | 2023-05-30 | University Of Kentucky Research Foundation | Devices and methods for removing perfluorinated compounds from contaminated water |
| CN115252571B (en) * | 2022-06-17 | 2023-09-22 | 南京大学 | Porous aminated organic fluorine capsule and preparation method and application thereof |
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