CN115252571A - 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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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
- A61K9/4816—Wall or shell material
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
- A61J3/00—Devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms
- A61J3/07—Devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms into the form of capsules or similar small containers for oral use
- A61J3/071—Devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms into the form of capsules or similar small containers for oral use into the form of telescopically engaged two-piece capsules
- A61J3/074—Filling capsules; Related operations
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
- A61J3/00—Devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms
- A61J3/07—Devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms into the form of capsules or similar small containers for oral use
- A61J3/071—Devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms into the form of capsules or similar small containers for oral use into the form of telescopically engaged two-piece capsules
- A61J3/077—Manufacturing capsule shells
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/32—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers, poly(meth)acrylates, or polyvinyl pyrrolidone
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/34—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyesters, polyamino acids, polysiloxanes, polyphosphazines, copolymers of polyalkylene glycol or poloxamers
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 an application of the porous aminated organic fluorine capsule in the adsorption of perfluorinated compounds, the porous aminated organic fluorine capsule is mixed with perfluorinated compounds, and the mixture is oscillated at a constant temperature of between 24 and 26 ℃, and the mass concentration ratio of the porous aminated organic fluorine capsule material to the perfluorinated compounds is 5 to 100. The porous organic fluorine capsule material is synthesized by a solvent displacement method based on common membrane materials of polyvinylidene fluoride, pore-forming agent polyvinylpyrrolidone and self-made aminated phenolic resin, and the efficient selective removal of the anionic perfluorinated compounds is successfully realized under the synergistic action of the organic fluorine shell of the capsule and the aminated phenolic resin in the capsule, and the raw materials are cheap and easy to obtain, and the preparation is simple and convenient.
Description
Technical Field
The invention belongs to capsules and a preparation method and application thereof, and particularly relates to a porous aminated organic fluorine capsule and a preparation method and application thereof.
Background
Perfluorinated compounds (PFCs) are novel synthetic fluorides with surfactant property, and have an alkyl chain consisting of carbon-fluorine bonds as a skeleton, and different functional groups connected with an ionic head, wherein the chemical general formula is F (CF)2)n-R. Since the first synthesis of 3M company in the end of the 40 th 20 th century, PFCs have been widely used in various fields of human production and life due to their hydrophobic and lipophobic properties, high temperature resistance, and strong oxidation resistance. Research shows that PFCs are universally present in global environment due to the large amount of use and strong stability of PFCs, and the concentration of PFCs in surface water and underground water can reach 1 mg.L at most-1. Among more than 3000 PFCs put on the market, perfluorooctanoic acid (PFOA) is the most representative, and not only is the PFCs produced and used in a large amount, but also is the final product of the transformation of the PFCs in the environment and organisms, and the detection frequency and the 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 four decades, the PFOA content in human serum has been increasing and the maximum concentration has reached 5 mug.L-1。
In order to eliminate the adverse effects of such pollutants on the environment and organisms, the laws for limiting the sale and use of PFOA have been issued, PFOA is also listed as a priority control list of persistent organic pollutants, and the health limiting concentration of PFOA in drinking water is 70 ng.L-1. For environmental and human health, PFASs removal techniques should be intensively studied.
Relevant researches show that the advanced reduction technology based on water and electrons and the advanced oxidation technology based on sulfate radicals can effectively treat high-concentration PFOA polluted wastewater, but have poor removal effect on trace PFOA in the water body of the practical environment. Therefore, if the trace amount of PFOA in the water body is to be subjected to innocent treatment, the PFOA is subjected to selective adsorption concentration firstly.
At present, the traditional adsorption technologies (activated carbon, ion exchange resin, mineral materials) and the like on the market have low removal efficiency on the pollutants 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, easy generation of secondary pollution and the like still exist.
Therefore, the development of an adsorbing material which is low in cost, easy to separate and capable of selectively adsorbing trace PFOA in an actual environmental water body is urgently needed.
Disclosure of Invention
The purpose of the invention is as follows: in order to overcome the defects in the prior art, the invention aims to provide a porous aminated organic fluorine capsule, another aim of the invention is to provide a preparation method of the porous aminated organic fluorine capsule, and still another aim of the invention is to provide the application of the porous aminated organic fluorine capsule in the adsorption of 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 pores on 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.
Further, the diameter of the porous aminated organofluorine capsule is 1.5-1.8 mm.
The preparation method of the porous aminated organofluorine 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 h, 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 uniformly disperse and remove air bubbles 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 by using an injector while stirring at the temperature of 25-30 ℃ to obtain a semi-cooked capsule;
and 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.
In S1, the mass ratio of ethylenediamine, formaldehyde and resorcinol is 1-3:1-3:1-2. In the alcohol-water mixed solution, the volume ratio of the ethanol to the water is 2:5.
In S2, the mass concentration ratio of polyvinylidene fluoride, polyvinylpyrrolidone and aminated phenol resin powder is 12. The weight average molecular weight of the polyvinylidene fluoride is 170000-190000. The weight average molecular weight of the polyvinylpyrrolidone is 1200000-1400000.
Further, in S3, the volume ratio of isopropyl alcohol to water in the mixture of water and isopropyl alcohol was 30%.
The application of the porous aminated organic fluorine capsule in the adsorption of perfluorinated compounds is that the porous aminated organic fluorine capsule is mixed with the perfluorinated compounds and is oscillated at the 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.
Further, the pH value of the porous aminated organic fluorine capsule mixed with the perfluorinated compound is adjusted to be 2-9.25, and the adsorption rate of the perfluorinated compound is more than 95%.
The adsorption principle is as follows: polyvinylidene fluoride with a structure similar to that of a 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 substances such as salt ions and the like and lipophilic organic substances such as humus and the like is effectively eliminated, and the selectivity of the perfluorinated compound is improved. The aminated phenolic resin can adsorb PFASs in the solution through electrostatic attraction, and the porous organic fluorine shell protects the aminated phenolic resin from interfering the adsorption of the PFASs.
Has the advantages that: compared with the prior art, the invention has the following remarkable characteristics:
1. based on common membrane material polyvinylidene fluoride, pore-forming agent polyvinylpyrrolidone and self-made aminated phenolic resin, the porous organic fluorine capsule material is synthesized by a solvent displacement method, and under the synergistic effect of the organic fluorine shell of the capsule and the aminated phenolic resin in the capsule, the high-efficiency selective removal of the anionic perfluorinated compound is successfully realized, the raw materials are cheap and easy to obtain, and the preparation process is simple and convenient to operate;
2. the porous aminated organic fluorine capsule material realizes the high-efficiency selective adsorption of perfluorinated compounds in a wide pH range, has good adaptability to strong acid and strong alkali environments, can still reach more than 95 percent of adsorption rate of the perfluorinated compounds even under strong alkali conditions, and can be used in extreme environments;
3. the porous aminated organic fluorine capsule material not only maintains the particle morphology of the traditional commercial activated carbon and ion exchange resin, but also does not reduce the retention time of the capsule in water treatment, and simultaneously has large particles and easy recovery;
4. the PFOA adsorption capacity recovery capsule has good reusability, the PFOA adsorption capacity of the capsule can be recovered through elution of a methanol solution, the PFOA adsorption capacity is almost unchanged after 5 times of repeated use, and the PFOA adsorption capacity recovery capsule has good economic applicability and bright prospect.
Drawings
FIG. 1 is a composite path diagram of the present invention;
FIG. 2 is a scanning electron microscope and a size distribution diagram of the present invention, wherein a is an electron microscope of aminated phenol resin under a scale of 1 μm, b is an electron microscope of aminated phenol resin under a scale of 200nm, c is a size distribution diagram of aminated phenol resin, d is an electron microscope of FC under a scale of 100 μm, e is an electron microscope of FC under a scale of 2 μm, f is a surface pore distribution diagram of FC, g is an electron microscope of AFC-1 under a scale of 100 μm, h is an electron microscope of AFC-1 under a scale of 200nm, i is a surface pore distribution diagram of AFC-1, j is an electron microscope of AFC-2 under a scale of 100 μm, k is an electron microscope of AFC-2 under a scale of 200nm, l is a surface pore distribution diagram of AFC-2, m is an electron microscope of AFC-3 under a scale of 100 μm, n is an electron microscope of AFC-3 under a scale of 200nm, and o is a surface pore distribution diagram of AFC-3;
FIG. 3 is a specific surface area profile of a porous aminated organic fluorine capsule material of the present invention;
FIG. 4 is a schematic infrared spectrum of a porous aminated organofluorine capsule material of the present invention;
FIG. 5 is a schematic zeta potential of a porous aminated organic fluorine capsule material of the present invention;
FIG. 6 is a thermal diagram of adsorption of PFOA by the porous aminated organic fluorine capsule material of the present invention, wherein a is the thermal diagram of adsorption of PFOA by ANP, and b is the thermal diagram of adsorption of PFOA by FC, AFC-1, AFC-2, AFC-3, AFC-4, AFC-5;
figure 7 is a comparison of the PFOA adsorption effect of different adsorbents of the present invention;
FIG. 8 is a graph of the adsorption kinetics of 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 of the porous aminated organic fluorine capsule material according to the present invention;
FIG. 10 is a graph of the influence of coexisting substances in different environments on PFOA adsorption of the porous aminated organic fluorine capsule material, wherein a is a graph of the influence of AFC-2 on PFOA adsorption, and b is a graph of the influence of ANP on PFOA adsorption;
FIG. 11 is a graph of the cyclic regeneration of the porous aminated organofluorine capsule material of the present invention.
Detailed Description
In the following examples, the weight average molecular weight of polyvinylidene fluoride was 170000 to 190000. The weight average molecular weight of the polyvinylpyrrolidone is 1200000-1400000.
Example 1
Referring to fig. 1, a preparation method of a porous aminated organic fluorine capsule material comprises the following steps:
s1, dissolving ethylenediamine, formaldehyde and resorcinol in a mass ratio of 1;
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;
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 step S2 into the solvent exchange solution by using an injector while stirring at the temperature of 25 ℃, and continuously stirring for 2 hours to obtain a semi-cooked capsule;
and S4, dispersing the semi-cooked capsules obtained in the S3 in pure water, stirring for 24 hours, and then carrying out vacuum drying in a vacuum drying oven at 100 ℃ for 12 hours to obtain porous aminated organic fluorine capsules, which are named AFC-1.
Example 2
A preparation method of a porous aminated organic fluorine capsule material comprises the following steps:
s1, dissolving ethylenediamine, formaldehyde and resorcinol in a mass ratio of 1;
s2, mixing PVDF, PVP and ANP, dispersing polyvinylidene fluoride, polyvinylpyrrolidone and aminated phenolic resin powder in DMF at a mass concentration ratio of 12;
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 step S2 into the solvent exchange solution by using an injector while stirring at the temperature of 25 ℃, and continuously stirring for 2 hours to obtain a semi-cooked capsule;
and S4, dispersing the semi-cooked capsules obtained in the S3 in pure water, stirring for 24 hours, and then carrying out vacuum drying in a vacuum drying oven at 100 ℃ for 12 hours to obtain porous aminated organic fluorine capsules, which are named AFC-2.
Example 3
A preparation method of a porous aminated organic fluorine capsule material comprises the following steps:
s1, dissolving ethylenediamine, formaldehyde and resorcinol in a mass ratio of 1;
s2, mixing PVDF, PVP and ANP, dispersing the mass concentration ratio of polyvinylidene fluoride to polyvinylpyrrolidone to aminated phenolic resin powder of 12;
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 step S2 into the solvent exchange solution by using an injector while stirring at the temperature of 25 ℃, and continuously stirring for 2 hours to obtain a semi-cooked capsule;
and S4, dispersing the semi-cooked capsules obtained in the step S3 in pure water, stirring for 24 hours, and then carrying out vacuum drying in a vacuum drying oven at 100 ℃ for 12 hours to obtain porous aminated organic fluorine capsules, which are named AFC-3.
Example 4
A preparation method of a porous aminated organic fluorine capsule material comprises the following steps:
s1, dissolving ethylenediamine, formaldehyde and resorcinol in a mass ratio of 1;
s2, mixing PVDF, PVP and ANP, dispersing polyvinylidene fluoride, polyvinylpyrrolidone and aminated phenolic resin powder in DMF at a mass concentration ratio of 12;
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 step S2 into the solvent exchange solution by using an injector while stirring at the temperature of 25 ℃, and continuously stirring for 2 hours to obtain a semi-finished capsule;
and S4, dispersing the semi-cooked capsules obtained in the S3 in pure water, stirring for 24 hours, and then carrying out vacuum drying in a vacuum drying oven at 100 ℃ for 12 hours to obtain porous aminated organic fluorine capsules, which are named AFC-4.
Example 5
A preparation method of a porous aminated organic fluorine capsule material comprises the following steps:
s1, dissolving ethylenediamine, formaldehyde and resorcinol in a mass ratio of 1;
s2, mixing PVDF, PVP and ANP, dispersing the mass concentration ratio of polyvinylidene fluoride to polyvinylpyrrolidone to aminated phenolic resin powder of 12;
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 step S2 into the solvent exchange solution by using an injector while stirring at the temperature of 25 ℃, and continuously stirring for 2 hours to obtain a semi-cooked capsule;
and S4, dispersing the semi-cooked capsules obtained in the S3 in pure water, stirring for 24 hours, and then carrying out vacuum drying in a vacuum drying oven at 100 ℃ for 12 hours to obtain porous aminated organic fluorine capsules, which are named AFC-5.
Comparative example
A preparation method of a porous aminated organic fluorine capsule material comprises the following steps:
s1, mixing PVDF, PVP and ANP, dispersing polyvinylidene fluoride and polyvinylpyrrolidone in DMF at a mass concentration ratio of 12;
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 an injector while stirring at the temperature of 25 ℃, and continuously stirring for 2 hours to obtain a semi-cooked capsule;
and S3, dispersing the semi-cooked capsules obtained in the S2 in pure water, stirring for 24 hours, and then carrying out vacuum drying in a vacuum drying oven at 100 ℃ for 12 hours to obtain porous aminated organic fluorine capsules, which are named as FC.
The ANP obtained in S1 of examples 1 to 5 was attached to a scanning electron microscope sample stage with a conductive adhesive, and the scanning electron microscope was used to photograph, as shown in fig. 2, it can be concluded that: ANP is uniform microspheres with the average diameter of 225.3nm, FC without ANP is white spheres with the diameter of 1.8-2 mm, and AFC-1-AFC-5 are yellow brown porous spheres with the diameter of 1.5-1.8 mm. The FC surface contained channels with an average pore size of 5.4 μm. The AFC-1 to AFC-4 surfaces also had abundant and uniform micropores, a pore diameter ranged from 28.6 to 330.5nm, and a pore diameter decreased with an increase in the content of ANP in the capsules, and no voids were observed in the ACF-5 surface.
Weighing the same mass of the porous aminated organofluorine capsules prepared in examples 1-5, respectively, in N2The adsorption and desorption instrument adopts a desorption mode to test the specific surface areas of different samples, and the test result is shown in figure 3. It can be concluded that: the specific surface area of ANP is 178.43m2g-1Specific surface area of FC 98.89m2g-1The 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, respectively2g-1The specific surface area increases and then decreases with increasing ANP content in the capsules, with AFC-2 having the greatest specific surface area.
The infrared signals of the selected samples were measured directly on a solid sample stage using multiple Attenuated Total Reflectance (ATR) mode using powder ANP, single particle FC and AFC, and the data is shown in fig. 4.
From this it can be concluded that: 2853.4 and 2925.6cm-1In the form of methyleneRadical (-CH)2-) the signal of stretching vibration comes from ANP where different porous aminated organofluorine capsules show stronger signals and increasing signal with increasing ANP content indicates increasing ANP content in the capsules. 1604.3cm-1Is the bending vibration signal of N-H bond in amino group, and the ANP shows strong signal at this place to indicate that the ANP is rich in amino group, and the signal of different porous aminated organofluorine capsules at this place is increased along with the increase of the ANP content to indicate that the content of the amino group in the capsules is increased continuously.
The porous aminated organofluorine capsule is characterized by a zeta-potential meter, and the specific steps are as follows:
(1) Are respectively configured to contain 1 g.L-1FC (comparative example) and ANP solution (example 1), adjusting the pH of the reaction solution to 2-11 with NaOH of different concentrations;
(2) Measuring the zeta potential of the solution obtained in the step (1) by using a zeta potential meter.
From this it can be concluded that: the isoelectric points of ANP and FC were 9.25 and 6.88, respectively, which indicates that ANP can attract anionic perfluoro compounds by electrostatic interaction over a wide pH range (pH = 2-9.25).
The method for investigating the adsorption thermodynamics of the porous aminated organic fluorine capsule on the PFOA comprises the following steps:
(1) Preparing 6 groups with initial concentration of 10-200 mg.L-1And 1 group of initial concentration of 10-900 mgL-15mL of each PFOA solution, pH of the reaction solution was adjusted to 6 with NaOH of different concentrations, 5mgFC, AFC-1, AFC-2, AFC-3, AFC-4, AFC-5 and ANP were added, the reaction solution was sealed and shaken in a constant temperature shaking cabinet, the reaction temperature was controlled at 25. + -. 1 ℃, and after 1 hour, two supernatants were each taken out as parallel samples to measure the PFOA concentration.
(2) Fitting the adsorption isotherm for PFOA using the Langmuir model, model Qe＝(KL×Qmax×Ce)/(1+KL×Ce) The maximum adsorption amounts of PFOA in ANP, FC and AFC-1 to AFC-5 were 0.64837, 0.00031, 0.01038, 0.04559, 0.04013, 0.03322 and 0.022, respectively78mgmg-1The specific results are shown in FIG. 7.
From this it can be concluded that: the adsorption capacity of ANP to PFOA is very strong, and the non-aminated capsule can not adsorb PFOA; the adsorption effect of the capsules with different raw material proportions on the PFOA is different, and the general rule is that the adsorption efficiency of the capsules on the PFOA is increased and then decreased along with the increase of the content of ANP. Wherein, the AFC-2 has the best adsorption effect on PFOA.
The adsorption of the porous aminated organic fluorine capsule AFC-2 with the strongest adsorption capacity and other adsorption materials on PFOA is considered, and the specific steps are as follows:
(1) The formulation contained 1. Mu.g L-15mL of PFOA solution, and adjusting the pH of the reaction solution to 6 by NaOH with different concentrations;
(2) Respectively adding 5mg of AFC-2, FC, ANP and powdered activated carbon into the solution obtained in the step (1), sealing, and oscillating by using a constant-temperature oscillation box, wherein the reaction temperature is controlled at 25 +/-1 ℃ and the reaction time is 5 hours. The sampling time is set to 0, 0.1, 0.3, 0.6, 1 and 5h respectively. Two supernatants were removed separately at each time point as parallel samples to determine the PFOA adsorption rate, as shown in figure 7.
From this it can be concluded that: the powder activated carbon and FC can hardly adsorb PFOA, AFC-2 and ANP have good PFOA adsorption effect, and 1 mu gL can be obtained in the first 1 hour-1The concentration of PFOA is reduced to 70ngL-1The following.
The method is characterized by inspecting the adsorption kinetic diagram of the porous aminated organic fluorine capsule on different perfluorinated compounds, and comprises the following specific steps:
(1) Each containing 1. Mu.g L of-15mL of a solution of trifluoroacetic acid (TFA), perfluorobutyric acid (PFBA), perfluorohexanoic acid (PFHxA), PFOA, perfluorooctane sulfonic acid (PFOS), hexafluoropropylene oxide trimer acid (HFPO-TA) and perfluorooctanedioic acid (PFdica), and adjusting the pH of the reaction solution to 6 with NaOH of various concentrations;
(2) And (2) respectively adding 5mg of AFC-2 into the solution obtained in the step (1), sealing, oscillating by using a constant-temperature oscillation box, controlling the reaction temperature to be 25 +/-1 ℃, and respectively taking out two supernatants as parallel samples after 1 hour to measure the adsorption efficiency.
From this it can be concluded that: the porous aminated organofluorine capsule has different adsorption effects on different perfluorinated compounds, has the best adsorption effect on PFOA, PFOS and HFPO-TA, and has the adsorption rate of more than 98 percent; the adsorption effect on TFA and PFdica is general.
The method for investigating the influence of pH on the adsorption of the perfluorinated compounds by the porous aminated organic fluorine capsule comprises the following specific steps:
(1) The formulation contained 1. Mu.g L-15mL of PFOA solution, adjusting the pH of the reaction solution to 2, 4, 6, 8 and 10 by NaOH with different concentrations;
(2) And (2) respectively adding 5mg of AFC-2 and ANP into the solution obtained in the step (1), sealing, oscillating by using a constant-temperature oscillation box, controlling the reaction temperature to be 25 +/-1 ℃, and respectively taking out two supernatants as parallel samples after 1 hour to measure the adsorption efficiency.
From this it can be concluded that: when pH is <8, pH has little influence on the process of adsorbing PFOA by AFC-2 and ANP, and when pH is >8, pH has a greater influence on the process of adsorbing PFOA by ANP and a smaller influence on the process of adsorbing PFOA by AFC-2.
Consider environmental coexisting substances humus (humic acid (SRHA), fulvic acid (SRFA)), small molecule acids (oxalic acid (OA), benzoic Acid (BA)), and salt ions (sodium chloride (NaCl), calcium chloride (CaCl)2) The specific steps of the method are as follows:
(1) Each containing 1. Mu.g L of-1PFOA and environment coexisting substance (5 mgL) of different concentrations-1SRHA、SRFA，5mgL-1NaCl、CaCl210mMOA, BA) solution 5mL, and adjusting the pH of the reaction solution to 6 by NaOH with different concentrations;
(2) Adding 5mg of AFC-2 and ANP into the solution obtained in the step (1), sealing, oscillating by using a constant-temperature oscillation box, controlling the reaction temperature to be 25 +/-1 ℃, and taking two supernatants as parallel samples to measure the adsorption efficiency after 1 hour and 5 hours. )
From this it can be concluded that: humus (SRHA, SRFA), small molecule acid (OA, BA) and saltIons (NaCl, caCl)2) Has great influence on the process of adsorbing PFOA by ANP and has little influence on the process of adsorbing PFOA by AFC-2.
The method for investigating the cyclic regeneration capacity of the porous aminated organic fluorine capsule comprises the following specific steps:
(1) Placing the porous aminated organic fluorine capsule saturated in adsorption into 5mL of methanol, sealing, oscillating by using a constant-temperature oscillation box, and controlling the reaction temperature to be 25 +/-1 ℃. Two supernatants were taken after 10 hours, respectively, as parallel samples to determine desorption efficiency.
(2) Taking out the desorbed porous aminated organic fluorine capsule, cleaning, drying and adsorbing 1 mu gL again-1PFOA, repeating the desorption process for 5 times, and comprehensively evaluating the cyclic regeneration efficiency of the capsule material.
From this it can be concluded that: the porous aminated organic fluorine capsule has strong cyclic regeneration capacity, and the adsorption capacity to PFOA is almost unchanged after 5 times of adsorption-desorption.
Example 6
A preparation method of a porous aminated organic fluorine capsule material comprises the following steps:
s1, dissolving ethylenediamine, formaldehyde and resorcinol in a mass ratio of 1;
s2, mixing PVDF, PVP and ANP, dispersing in DMF, and continuously stirring for 2 hours at 50 ℃ 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 step S2 into the solvent exchange solution by using an injector while stirring at the temperature of 25 ℃, and continuously stirring for 2 hours to obtain a semi-cooked capsule;
and S4, dispersing the semi-cooked capsule obtained in the S3 in pure water, stirring for 24 hours, and then carrying out vacuum drying in a vacuum drying oven at 90 ℃ for 12 hours to obtain the porous aminated organic fluorine capsule.
Example 7
A preparation method of a porous aminated organic fluorine capsule material comprises the following steps:
s1, dissolving ethylenediamine, formaldehyde and resorcinol in a mass ratio of 3;
s2, mixing PVDF, PVP and ANP, dispersing in DMF, and continuously stirring for 4 hours at 60 ℃ 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 step S2 into the solvent exchange solution by using an injector while stirring at the temperature of 30 ℃, and continuously stirring for 2 hours to obtain a semi-cooked capsule;
and S4, dispersing the semi-cooked capsule obtained in the S3 in pure water, stirring for 24 hours, and then carrying out vacuum drying in a vacuum drying oven at 100 ℃ for 12 hours to obtain the porous aminated organic fluorine capsule.
Example 8
A preparation method of a porous aminated organic fluorine capsule material comprises the following steps:
s1, dissolving ethylenediamine, formaldehyde and resorcinol in a mass ratio of 2;
s2, mixing PVDF, PVP and ANP, dispersing in DMF, and continuously stirring for 3 hours at 55 ℃ 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 step S2 into the solvent exchange solution by using an injector while stirring at the temperature of 27 ℃, and continuously stirring for 2 hours to obtain a semi-cooked capsule;
and S4, dispersing the semi-cooked capsule obtained in the S3 in pure water, stirring for 24 hours, and then carrying out vacuum drying in a vacuum drying oven at 95 ℃ for 12 hours to obtain the porous aminated organic fluorine capsule.
Claims (10)
1. A porous aminated organofluorine capsule characterized by: the composite material comprises a porous organic fluorine shell, wherein aminated phenolic resin is filled in the organic fluorine shell.
2. A porous aminated organofluorine capsule according to claim 1, wherein: 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 organofluorine capsule according to claim 1, wherein: the diameter of the porous aminated organic fluorine capsule is 1.5-1.8 mm.
4. A method for preparing a porous aminated organofluorine capsule according to any one of claims 1 to 3, characterized by comprising the steps of:
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 h, 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, taking 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 while stirring at the temperature of 25-30 ℃ to obtain a semi-cooked capsule;
and 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.
5. The method for preparing a porous aminated organofluorine capsule according to claim 4, wherein: in the S1, the mass ratio of ethylenediamine, formaldehyde and resorcinol is 1-3:1-3:1-2.
6. The method for preparing a porous aminated organofluorine capsule according to claim 4, wherein: in the S2, the mass concentration ratio of polyvinylidene fluoride, polyvinylpyrrolidone and aminated phenolic resin powder is 12.
7. The method for preparing a porous aminated organofluorine capsule according to claim 4, wherein: in S2, the weight-average molecular weight of polyvinylidene fluoride is 170000-190000.
8. The method for preparing porous aminated organofluorine capsule according to claim 4, characterized in that: in the S2, the weight average molecular weight of the polyvinylpyrrolidone is 1200000-1400000.
9. Use of a porous aminated organofluorine capsule according to any one of claims 1-3 for the adsorption of perfluorinated compounds, characterized in that: mixing the porous aminated organic fluorine capsule with a 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.
10. The use of a porous aminated organofluorine capsule according to claim 9 for adsorbing perfluorochemicals, wherein: the pH value of the porous aminated organic fluorine capsule mixed with the perfluorinated compound is adjusted to 2-9.25, and the adsorption rate of the perfluorinated compound is more than 95%.
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| WO2023241689A1 (en) * | 2022-06-17 | 2023-12-21 | 南京大学 | Porous aminated organic fluorine capsule, preparation method therefor and use thereof |
| CN117482932A (en) * | 2023-09-26 | 2024-02-02 | 湖南中寅环保设备制造有限公司 | Regeneration method of waste lubricating oil refined adsorbent |
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