CN114951237B - Method for degrading micro-nano plastic - Google Patents
Method for degrading micro-nano plastic Download PDFInfo
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- CN114951237B CN114951237B CN202210503133.5A CN202210503133A CN114951237B CN 114951237 B CN114951237 B CN 114951237B CN 202210503133 A CN202210503133 A CN 202210503133A CN 114951237 B CN114951237 B CN 114951237B
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- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 9
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- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B2101/00—Type of solid waste
- B09B2101/75—Plastic waste
- B09B2101/77—Plastic waste containing chlorine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B2101/00—Type of solid waste
- B09B2101/75—Plastic waste
- B09B2101/78—Plastic waste containing foamed plastics, e.g. polystyrol
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- General Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
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- Treatments Of Macromolecular Shaped Articles (AREA)
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Abstract
The invention provides a method for degrading micro-nano plastic, which comprises the following steps of degrading the micro-nano plastic by using a Fenton reagent at a temperature of between 80 ℃ below zero and 5 ℃ below zero; wherein, in the Fenton reagent, fe 2+ And/or Fe 3+ The concentration is 0.01-120 mu mol/L, and the volume fraction of the hydrogen peroxide is 0.001-0.05%. Compared with the prior art, the method for degrading the micro-nano plastic realizes the efficient degradation of the micro-nano plastic by the low-concentration Fenton reagent; the degradation effect on micro-nano plastics is good; the method also has the characteristics of low price, green chemistry and strong applicability.
Description
Technical Field
The invention relates to the field of solid waste pollution control, in particular to a method for degrading micro-nano plastics.
Background
The plastic has stable physical and chemical properties and low cost, and is often used once, thereby causing white pollution. The plastic is gradually weakened under the action of chemical aging, microbial aging or photoaging, and then is decomposed into small micro-nano plastic blocks. The physicochemical properties of the micro-nano plastics are very stable, and the micro-nano plastics are widely distributed in sediments, rivers, sewage, atmosphere and soil, especially in water environment. Nowadays, micro-nano plastics have attracted extensive attention, become common solid waste and cause serious pollution to the environment.
In a method for degrading an organic polymer compoundThe chemical degradation method has the advantages of high efficiency and easy degradation. Currently, with respect to chemical degradation of plastics, the core is degradation of the plastics by strongly oxidizing substances. Among them, the fenton method has an excellent characteristic of providing a strongly oxidizing substance. However, the conventional Fenton method requires a high concentration of Fe 2+ And/or Fe 3+ The mixed solution of the micro-nano plastic and hydrogen peroxide is carried out at a relatively high temperature, but the degradation efficiency is extremely low, and organic matters on the surface of the plastic can be removed, but the micro-nano plastic is not degraded.
In view of the above, there is a need to provide a method for degrading micro-nano plastics, so as to solve or at least alleviate the technical defect that the general fenton method can only remove organic matters on the surface of plastics, but not degrade the micro-nano plastics.
Disclosure of Invention
The invention mainly aims to provide a method for degrading micro-nano plastic, aiming at solving the problem that the prior art can only remove organic matters on the surface of the plastic, but not degrade the micro-nano plastic; and the consumption of chemical reagents is large.
In order to realize the aim, the invention provides a method for degrading micro-nano plastic, which adopts Fenton reagent to degrade the micro-nano plastic at the temperature of-80 to-5 ℃;
wherein, in the Fenton reagent, fe 2+ And/or Fe 3+ The concentration is 0.01-120 mu mol/L, and the volume fraction of the hydrogen peroxide is 0.001-0.05%.
The method for degrading the micro-nano plastic is characterized in that the preparation step of the Fenton reagent comprises the following steps:
s1, providing said Fe 2+ And/or Fe 3+ To the solution of Fe 2+ And/or Fe 3+ Adding the hydrogen peroxide into the solution to obtain a mixed solution;
and S2, adjusting the pH value of the mixed solution to 2-12 to obtain the Fenton reagent.
Further, in the step S1, the Fe 2+ And/or Fe 3+ Sources include: ferrous salts, ferric salts or mixtures of ferrous and ferric salts. The ferrous salt includes: ferrous sulfate or chlorineFerrous iron melting; the iron salts include: iron sulfate, iron nitrate or iron chloride.
The method for degrading the micro-nano plastic comprises the following steps: one or more of Polystyrene (PS), polycarbonate (PC), polyethylene terephthalate (PET), nylon (PA), polyethylene (PE), polypropylene (PP), and polyvinyl chloride (PVC).
The method for degrading the micro-nano plastic comprises the following steps: 10-5000nm.
The method for degrading the micro-nano plastic, wherein the solid-to-liquid ratio of the micro-nano plastic to the Fenton reagent is as follows: 1-5mg.
The main technical principle involved in the invention comprises:
1. firstly, it is understood that the micro-nano plastic has stable physicochemical properties and is difficult to degrade, a chemical oxidation means (such as a fenton reagent) generally adopted in the prior art can only remove small molecular impurities attached to the surface of the micro-nano plastic in the environment, and the degradation of the macromolecular organic matter of the micro-nano plastic is difficult to realize.
However, different from the prior art, the method for degrading the micro-nano plastic provided by the invention adopts a frozen low-concentration Fenton reagent, and aims to realize efficient degradation of the micro-nano plastic, and especially can realize degradation of the micro-nano plastic.
2. Secondly, it is clear that the freezing technology adopted by the method for degrading the micro-nano plastic in the invention can realize the concentration of the low-concentration Fenton reagent to generate hydroxyl free radical (. OH) and singlet Oxygen (OH) 1 O 2 ) And hydrogen peroxide (H) 2 O 2 ) The oxidizing property of the active Oxygen (ROS) components is enhanced; the pH enhancement brought by the freezing technology can further realize the oxidative enhancement of the Fenton reagent so as to realize the degradation reaction of the micro-nano plastic.
3. The degradation method of the micro-nano plastic is carried out at the temperature of-80 to-5 ℃. At the temperature, the micro-nano plastic in the water body can be concentrated, so that the micro-nano plastic generates self-crosslinking action and forms an active site;
meanwhile, at the temperature, the space distance between the Fenton reagent and the micro-nano plastic is extremely shortened, and under the combined action of a series of physical and chemical changes such as the Fenton reagent with strong oxidizing property and the change of the space structure, the original stable chemical state of the micro-nano plastic is destroyed, so that the degradation of micro-nano plastic macromolecules difficult to degrade is realized, and the purpose of efficient degradation is achieved.
In addition, it needs to be emphasized that the high-efficiency degradation of the micro-nano plastic with low concentration in the water body is realized through the synergistic effect and the cooperation of the above mechanisms.
Compared with the prior art, the invention has at least the following advantages:
1. the efficient degradation of the micro-nano plastic by the low-concentration Fenton reagent is realized.
2. Has good degradation effect on micro-nano plastics. Specifically, the micro surface of the micro-nano plastic treated by the micro-nano plastic degradation method is rough and irregular, and more oxygen-containing functional groups are added, namely the carbon-oxygen ratio is increased.
3. Low cost, green chemistry and strong applicability. Firstly, the Fenton reagent used in the method for degrading the micro-nano plastic adopts low-concentration Fe 2+ And/or Fe 3+ And the hydrogen peroxide is prepared from the raw materials, is a common inorganic chemical product and has low price. Second, enrichment and concentration occur only in the frozen state, and low concentration of Fe after thawing 2+ And/or Fe 3+ Has small influence on environment and low concentration of Fe 2+ And/or Fe 3+ The fertilizer is also a nutrient component of aquatic animals and plants, and is an important component of a water environment. The environment inherently contains low-concentration hydrogen peroxide and can be further decomposed into water and oxygen to enter the geochemical cycle. Thirdly, the industrial condition of the freezing temperature range at the present stage is easy to realize, and the large-volume water body can be treated without restriction.
Drawings
In order to more clearly illustrate the embodiments or technical solutions of the present invention, the drawings used in the embodiments or technical solutions of the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is a Transmission Electron Microscope (TEM) image of the motion trend of the micro-nano plastic in analysis example 1; wherein, (a) is a TEM image of polystyrene at normal temperature, and (b) is a TEM image of polystyrene after freezing;
FIG. 2 is a Scanning Electron Microscope (SEM) image of a micro-nano plastic original sample, a product after reaction of the micro-nano plastic processed at normal temperature and a product after degradation of the micro-nano plastic processed by freezing in example 1; wherein, (a) is an SEM image of a micro-nano plastic original sample, (b) is an SEM image of a product obtained after the reaction of the micro-nano plastic processed at normal temperature, and (c) is an SEM image of a product obtained after the degradation of the micro-nano plastic processed by freezing;
FIG. 3 is a Scanning Electron Microscope (SEM) image of a micro-nano plastic original sample, a product obtained after reaction of the micro-nano plastic processed at normal temperature and a product obtained after degradation of the micro-nano plastic processed by freezing in example 2; wherein, (a) is an SEM image of a micro-nano plastic original sample, (b) is an SEM image of a product obtained after the reaction of the micro-nano plastic processed at normal temperature, and (c) is an SEM image of a product obtained after the degradation of the micro-nano plastic processed by freezing;
FIG. 4 is a graph comparing the O/C ratio changes of the original micro-nano plastic sample, the product after the reaction of the micro-nano plastic processed at normal temperature and the product after the degradation of the micro-nano plastic processed by freezing in examples 1 to 9.
The implementation, functional features and advantages of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
It should be noted that the features in the following embodiments and examples may be combined with each other without conflict. It is also to be understood that the terminology used in the examples herein is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs and the description of the present invention, and any methods, apparatuses, and materials similar or equivalent to those described in the examples of the present invention may be used to practice the present invention. It will be appreciated by those skilled in the art that, as an illustration of the present document, the "O/C ratio" can be expressed as the ratio between oxygen and carbon, TEM as a transmission electron microscope, SEM as a scanning electron microscope, and XPS as an X-ray photoelectron spectroscopy, without affecting the practical understanding of the present solution.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Test methods in which specific conditions are not noted in the following examples are generally performed under conventional conditions or conditions recommended by each manufacturer. The materials or reagents required in the following examples are commercially available unless otherwise specified.
In the attached drawings, 1 is a micro-nano plastic degraded under the condition of example 1 adopted in degradation, 2 is a micro-nano plastic degraded under the condition of example 2 adopted in degradation, 3 is a micro-nano plastic degraded under the condition of example 3 adopted in degradation, 4 is a micro-nano plastic degraded under the condition of example 4 adopted in degradation, 5 is a micro-nano plastic degraded under the condition of example 5 adopted in degradation, 6 is a micro-nano plastic degraded under the condition of example 6 adopted in degradation, 7 is a micro-nano plastic degraded under the condition of example 7 adopted in degradation, 8 is a micro-nano plastic degraded under the condition of example 8 adopted in degradation, 9 is a micro-nano plastic degraded under the condition of example 9 adopted in degradation, an original sample is an O/C ratio corresponding to an original sample of the micro-nano plastic in each example, normal-temperature treatment is an O/C ratio corresponding to a reaction product of the micro-nano plastic treated at normal temperature, and freezing treatment is an O/C ratio corresponding to a degradation product of the micro-nano plastic treated at normal temperature in each example.
In order to effectively and efficiently degrade micro-nano plastics, the invention provides a degradation method of micro-nano plastics, which specifically comprises the steps of degrading the micro-nano plastics by using a Fenton reagent at a temperature of between 80 ℃ below zero and 5 ℃ below zero;
wherein, in the Fenton reagent, fe 2+ And/or Fe 3+ The concentration is 0.01-120 mu mol/L, and the volume fraction of the hydrogen peroxide is 0.001-0.05%. It will be appreciated by those skilled in the art that the Fenton reagent has strong oxidizing properties and that the Fe in the Fenton reagent is 2+ And/or Fe 3+ The catalyst mainly plays a role in catalyzing the degradation of the micro-nano plastic.
And, as will be known to those skilled in the art, the micro-nano plastic refers to plastic with three-dimensional size less than 5mm, and the particle size of the micro-nano plastic may be 10-5000nm.
In the method for degrading the micro-nano plastic, the preparation steps of the Fenton reagent adopted by the method comprise:
s1, providing said Fe 2+ And/or Fe 3+ To the solution of Fe 2+ And/or Fe 3+ Adding the hydrogen peroxide into the solution to obtain a mixed solution; wherein in the mixed solution, fe 2+ And/or Fe 3+ The concentration is 0.01-120 mu mol/L, and the volume fraction of the hydrogen peroxide is 0.001-0.05%.
And S2, adjusting the pH value of the mixed solution to 2-12 to obtain the Fenton reagent.
It should be noted that in the process of degrading micro-nano plastic in a laboratory, a certain amount of micro-nano plastic microspheres are weighed and added into a reaction container, the prepared Fenton reagent is added into the reaction container, the reaction temperature is controlled to be-80 to-5 ℃, and degradation reaction is carried out for a period of time.
In the step S1, the Fe 2+ And/or Fe 3+ Sources include: ferrous salts, ferric salts or mixtures of ferrous and ferric salts. The ferrous salt includes: ferrous sulfate or ferrous chloride; the iron salts include: iron sulfate, iron nitrate or iron chloride.
The micro-nano plastic comprises the following materials: one or more of Polystyrene (PS), polycarbonate (PC), polyethylene terephthalate (PET), nylon (PA), polyethylene (PE), polypropylene (PP), and polyvinyl chloride (PVC).
For a further understanding of the present invention, there will now be illustrated:
example 1
A method for degrading micro-nano plastics comprises the following steps:
1. preparation of Fenton reagent
By using FeSO 4 ·7H 2 Preparing a mixed solution from O and hydrogen peroxide, so that the concentration of the iron element in the mixed solution is 30 mu mol/L, and the volume fraction of the hydrogen peroxide is 0.0015%; and adjusting the pH of the mixed solution =4 to obtain a fenton reagent.
2. Preparing polystyrene micro-nano plastic
2.5mg of polystyrene microspheres (with a particle size of about 600 nm) were weighed and added to a reaction vessel. The O/C ratio of the polystyrene microspheres (raw sample) was measured using X-ray photoelectron spectroscopy (XPS), as shown in fig. 4; the SEM image of the polystyrene microspheres (original sample) is shown with reference to fig. 2 (a).
3. Freezing treatment
(1) Measuring 100mL of the Fenton reagent in the step 1, and adding the Fenton reagent into a reaction container filled with 2.5mg of polystyrene microspheres (see the step 2); the reaction temperature was controlled at-20 ℃ and the reaction time was 1.5 days.
(2) And washing the degraded product with ultrapure water, and draining to obtain the frozen micro-nano plastic degraded product. Measuring the O/C ratio of the degraded product of the frozen micro-nano plastic by using X-ray photoelectron spectroscopy (XPS), wherein the O/C ratio is shown in figure 4; an SEM image of a product obtained after the freezing treatment of the micro-nano plastic is degraded is shown in a figure 2 (c).
4. Normal temperature treatment (comparative reaction)
(1) Measuring 100mL of the Fenton reagent in the step 1, and adding the Fenton reagent into a reaction container filled with 2.5mg of polystyrene microspheres (see the step 2); the reaction time was 1.5 days.
(2) Washing the degraded product with ultrapure water, and draining to obtain the micro-nano plastic reaction product treated at normal temperature. The O/C ratio of the product after the reaction was measured using X-ray photoelectron spectroscopy (XPS), as shown in FIG. 4; an SEM image of a product after the reaction of the normal-temperature treated micro-nano plastic is shown in a figure 2 (b).
Example 2
A method for degrading micro-nano plastics comprises the following steps:
1. preparation of Fenton reagent
By using FeSO 4 ·7H 2 Preparing a mixed solution from O and hydrogen peroxide, so that the concentration of the iron element in the mixed solution is 30 mu mol/L, and the volume fraction of the hydrogen peroxide is 0.0015%; and adjusting the pH of the mixed solution =4 to obtain a fenton reagent.
2. Preparing polystyrene micro-nano plastic
2.5mg of polystyrene microspheres (with a particle size of about 600 nm) were weighed and added to a reaction vessel. The O/C ratio of the polystyrene microspheres (raw sample) was measured using X-ray photoelectron spectroscopy (XPS), as shown in fig. 4; SEM image of the polystyrene microspheres (original sample) is shown in fig. 3 (a).
3. Freezing treatment
(1) Measuring 100mL of the Fenton reagent in the step 1, and adding the Fenton reagent into a reaction container filled with 2.5mg of polystyrene microspheres (see the step 2); the reaction temperature was controlled at-20 ℃ and the reaction time was 6 days.
(2) And washing the degraded product with ultrapure water, and draining to obtain the frozen micro-nano plastic degraded product. Measuring the O/C ratio of the degraded product of the frozen micro-nano plastic by using X-ray photoelectron spectroscopy (XPS), wherein the O/C ratio is shown in figure 4; an SEM image of a degraded product of the frozen micro-nano plastic is shown in a reference figure 3 (c).
4. Normal temperature treatment (contrast reaction)
(1) Measuring 100mL of the Fenton reagent in the step 1, and adding the Fenton reagent into a reaction container filled with 2.5mg of polystyrene microspheres (see the step 2); the reaction time was 6 days.
(2) Washing the degraded product with ultrapure water, and draining to obtain the product of the reaction of the micro-nano plastic treated at normal temperature. The O/C ratio of the product after the reaction was measured using X-ray photoelectron spectroscopy (XPS), as shown in FIG. 4; an SEM image of a product after the reaction of the normal-temperature treated micro-nano plastic is shown in a figure 3 (b).
Example 3
A method for degrading micro-nano plastics comprises the following steps:
1. preparation of Fenton reagent
Using FeCl 3 ·6H 2 Preparing a mixed solution by using O and hydrogen peroxide, wherein the concentration of iron element in the mixed solution is 120 mu mol/L, and the volume fraction of the hydrogen peroxide is 0.02%; and adjusting the pH of the mixed solution =5 to obtain a fenton reagent.
2. Preparing polypropylene micro-nano plastic
2.5mg of polypropylene microspheres (with a particle size of about 3000 nm) are weighed and added into a reaction vessel. The O/C ratio of the polypropylene microspheres (raw sample) was measured using X-ray photoelectron spectroscopy (XPS), as shown in fig. 4.
3. Freezing treatment
(1) Measuring 100mL of the Fenton reagent in the step 1, and adding the Fenton reagent into a reaction container filled with 2.5mg of polypropylene microspheres (see the step 2); the reaction temperature was controlled at-40 ℃ and the reaction time was 15 days.
(2) And washing the degraded product with ultrapure water, and draining to obtain the frozen micro-nano plastic degraded product. And measuring the O/C ratio of the degraded product of the frozen micro-nano plastic by using X-ray photoelectron spectroscopy (XPS), as shown in figure 4.
4. Normal temperature treatment (contrast reaction)
(1) Measuring 100mL of the Fenton reagent in the step 1, and adding the Fenton reagent into a reaction container filled with 2.5mg of polypropylene microspheres (see the step 2); the reaction time was 15 days.
(2) Washing the degraded product with ultrapure water, and draining to obtain the product of the reaction of the micro-nano plastic treated at normal temperature. The O/C ratio of the product after the reaction was measured using X-ray photoelectron spectroscopy (XPS), as shown in FIG. 4.
Example 4
A method for degrading micro-nano plastics comprises the following steps:
1. preparation of Fenton's reagent
Using FeCl 2 ·4H 2 Preparing a mixed solution from O and hydrogen peroxide, so that the concentration of iron element in the mixed solution is 30 mu mol/L, and the volume fraction of hydrogen peroxide is 0.02%; and adjusting the pH of the mixed solution =6 to obtain a fenton reagent.
2. Preparing polyethylene micro-nano plastic
2.5mg of polyethylene microspheres (with a particle size of about 3000 nm) are weighed and added into a reaction vessel. The O/C ratio of the polyethylene microspheres (raw sample) was measured using X-ray photoelectron spectroscopy (XPS), as shown in fig. 4.
3. Freezing treatment
(1) Measuring 100mL of the Fenton reagent in the step 1, and adding the Fenton reagent into a reaction container filled with 2.5mg of polyethylene microspheres (see the step 2); the reaction temperature was controlled at-30 ℃ and the reaction time was controlled at 2 days.
(2) And washing the degraded product with ultrapure water, and draining to obtain the frozen micro-nano plastic degraded product. And measuring the O/C ratio of the degraded product of the frozen micro-nano plastic by using X-ray photoelectron spectroscopy (XPS), as shown in figure 4.
4. Normal temperature treatment (comparative reaction)
(1) Measuring 100mL of the Fenton reagent in the step 1, and adding the Fenton reagent into a reaction container filled with 2.5mg of polyethylene microspheres (see the step 2); the reaction time was 2 days.
(2) Washing the degraded product with ultrapure water, and draining to obtain the micro-nano plastic reaction product treated at normal temperature. The O/C ratio of the product after the reaction was measured using X-ray photoelectron spectroscopy (XPS), as shown in FIG. 4.
Example 5
A method for degrading micro-nano plastics comprises the following steps:
1. preparation of Fenton reagent
Using FeCl 2 ·4H 2 Preparing a mixed solution from O and hydrogen peroxide, so that the concentration of iron element in the mixed solution is 20 mu mol/L, and the volume fraction of hydrogen peroxide is 0.015%; and adjusting the pH of the mixture =9 to obtain a fenton reagent.
2. Preparing micro-nano plastic mixed with polyethylene and polypropylene
Weighing 2.5mg of micro-nano plastic obtained by mixing polyethylene (with the particle size of about 3000 nm) and polypropylene (with the particle size of about 3000 nm) according to the mass ratio of 1:1, and adding the micro-nano plastic mixed with the polyethylene and the polypropylene into a reaction container. The O/C ratio of the polyethylene and polypropylene mixed micro-nano plastic (original sample) was measured using X-ray photoelectron spectroscopy (XPS), as shown in fig. 4.
3. Freezing treatment
(1) Measuring 100mL of the Fenton reagent in the step 1, and adding the Fenton reagent into a reaction container filled with 2.5mg of micro-nano plastic mixed by polyethylene and polypropylene (see the step 2); the reaction temperature was controlled at-80 ℃ and the reaction time was 30 days.
(2) And washing the degraded product with ultrapure water, and draining to obtain the frozen micro-nano plastic degraded product. And measuring the O/C ratio of the degraded product of the frozen micro-nano plastic by using X-ray photoelectron spectroscopy (XPS), as shown in figure 4.
4. Normal temperature treatment (comparative reaction)
(1) Measuring 100mL of the Fenton reagent in the step 1, and adding the Fenton reagent into a reaction container filled with 2.5mg of micro-nano plastic mixed by polyethylene and polypropylene (see the step 2); the reaction time was 30 days.
(2) Washing the degraded product with ultrapure water, and draining to obtain the product of the reaction of the micro-nano plastic treated at normal temperature. The O/C ratio of the product after the reaction was measured using X-ray photoelectron spectroscopy (XPS), as shown in FIG. 4.
Example 6
A method for degrading micro-nano plastics comprises the following steps:
1. preparation of Fenton reagent
Using FeCl 3 ·6H 2 Preparing mixed solution of O and hydrogen peroxideThe concentration of the iron element in the mixed solution is 0.01 mu mol/L, and the volume fraction of the hydrogen peroxide is 0.01 percent; and adjusting the pH of the mixture =12 to obtain a fenton reagent.
2. Preparing micro-nano plastic mixed by polyvinyl chloride, polyethylene and polypropylene
Weighing 2.5mg of micro-nano plastic obtained by mixing polyvinyl chloride (with the particle size of about 3000 nm), polyethylene (with the particle size of about 3000 nm) and polypropylene (with the particle size of about 3000 nm) according to a mass ratio of 4. The O/C ratio of the polyvinyl chloride, polyethylene and polypropylene mixed micro-nano plastic (original sample) was measured using X-ray photoelectron spectroscopy (XPS), as shown in fig. 4.
3. Freezing treatment
(1) Measuring 100mL of the Fenton reagent in the step 1, and adding the Fenton reagent into a reaction container filled with 2.5mg of micro-nano plastic mixed by polyvinyl chloride, polyethylene and polypropylene (see the step 2); the reaction temperature was controlled at-5 ℃ and the reaction time was 300 days.
(2) And washing the degraded product with ultrapure water, and draining to obtain the frozen micro-nano plastic degraded product. And measuring the O/C ratio of the degraded product of the frozen micro-nano plastic by using X-ray photoelectron spectroscopy (XPS), wherein the O/C ratio is shown in figure 4.
4. Normal temperature treatment (contrast reaction)
(1) Measuring 100mL of the Fenton reagent in the step 1, and adding the Fenton reagent into a reaction container filled with 2.5mg of micro-nano plastic mixed by polyvinyl chloride, polyethylene and polypropylene (see the step 2); the reaction time was 300 days.
(2) Washing the degraded product with ultrapure water, and draining to obtain the product of the reaction of the micro-nano plastic treated at normal temperature. The O/C ratio of the product after the reaction was measured using X-ray photoelectron spectroscopy (XPS), as shown in FIG. 4.
Example 7
A method for degrading micro-nano plastics comprises the following steps:
1. preparation of Fenton's reagent
Using FeCl 3 ·6H 2 Preparing a mixed solution from O and hydrogen peroxide, wherein the concentration of iron in the mixed solution is 0.05 mu mol/L, and the volume fraction of the hydrogen peroxide is 0.05%; and adjusting the pH =2 of the mixed solution to obtain a fenton reagent.
2. Preparing micro-nano plastic mixed by polycarbonate, polyethylene terephthalate and nylon
Weighing 2.5mg of micro-nano plastic obtained by mixing polycarbonate (with the particle size of about 1000 nm), polyethylene terephthalate (with the particle size of about 2000 nm) and nylon (with the particle size of about 4000 nm) according to a mass ratio of 1. The O/C ratio of the polycarbonate, polyethylene terephthalate and nylon mixed micro-nano plastics (original sample) was measured using X-ray photoelectron spectroscopy (XPS), as shown in fig. 4.
3. Freezing treatment
(1) Measuring 100mL of the Fenton reagent in the step 1, and adding the Fenton reagent into a reaction container filled with 2.5mg of micro-nano plastic mixed by polycarbonate, polyethylene terephthalate and nylon (see the step 2); the reaction temperature was controlled at-5 ℃ and the reaction time was controlled at 0.5 day.
(2) And washing the degraded product with ultrapure water, and draining to obtain the frozen micro-nano plastic degraded product. And measuring the O/C ratio of the degraded product of the frozen micro-nano plastic by using X-ray photoelectron spectroscopy (XPS), wherein the O/C ratio is shown in figure 4.
4. Normal temperature treatment (contrast reaction)
(1) Measuring 100mL of the Fenton reagent in the step 1, and adding the Fenton reagent into a reaction container filled with 2.5mg of micro-nano plastic mixed by polycarbonate, polyethylene terephthalate and nylon (see the step 2); the reaction time was 0.5 day.
(2) Washing the degraded product with ultrapure water, and draining to obtain the product of the reaction of the micro-nano plastic treated at normal temperature. The O/C ratio of the product after the reaction was measured using X-ray photoelectron spectroscopy (XPS), as shown in FIG. 4.
Example 8
A method for degrading micro-nano plastics comprises the following steps:
1. preparation of Fenton's reagent
Using Fe (NO) 3 ) 3 ·9H 2 Preparing a mixed solution from O and hydrogen peroxide, wherein the concentration of iron in the mixed solution is 0.05 mu mol/L, and the volume fraction of the hydrogen peroxide is 0.05%; and adjusting the pH of the mixture =9 to obtain a fenton reagent.
2. Preparation of polyvinyl chloride micro-nano plastic
Weighing 2.5mg of polyvinyl chloride micro-nano plastic (the particle size is about 3000 nm), and adding the polyvinyl chloride micro-nano plastic into a reaction container. The O/C ratio of the polyvinyl chloride micro-nano plastic (original sample) was measured using X-ray photoelectron spectroscopy (XPS), as shown in fig. 4.
3. Freezing treatment
(1) Measuring 100mL of the Fenton reagent in the step 1, and adding the Fenton reagent into a reaction container filled with 2.5mg of polyvinyl chloride micro-nano plastic (see the step 2); the reaction temperature was controlled at-50 ℃ and the reaction time was controlled at 120 days.
(2) And washing the degraded product with ultrapure water, and draining to obtain the frozen micro-nano plastic degraded product. And measuring the O/C ratio of the degraded product of the frozen micro-nano plastic by using X-ray photoelectron spectroscopy (XPS).
4. Normal temperature treatment (comparative reaction)
(1) Measuring 100mL of the Fenton reagent in the step 1, and adding the Fenton reagent into a reaction container filled with 2.5mg of polyvinyl chloride micro-nano plastic (see the step 2); the reaction time was 120 days.
(2) Washing the degraded product with ultrapure water, and draining to obtain the product of the reaction of the micro-nano plastic treated at normal temperature. The O/C ratio of the product after the reaction was measured using X-ray photoelectron spectroscopy (XPS), as shown in FIG. 4.
Example 9
A method for degrading micro-nano plastics comprises the following steps:
1. preparation of Fenton's reagent
Using Fe 2 (SO 4 ) 3 ·xH 2 Preparing a mixed solution from O and hydrogen peroxide to ensure that the concentration of the iron element in the mixed solution is 0.015 mu mol/L, and the hydrogen peroxideIs 0.05%; and adjusting the pH of the mixture =9 to obtain a fenton reagent.
2. Preparing polycarbonate micro-nano plastic
Weighing 2.5mg of polycarbonate micro-nano plastic (the particle size is about 1000 nm), and adding the polycarbonate micro-nano plastic into a reaction container. The O/C ratio of the polycarbonate micro-nano plastic (original sample) was measured by X-ray photoelectron spectroscopy (XPS), as shown in FIG. 4.
3. Freezing treatment
(1) Measuring 100mL of the Fenton reagent in the step 1, and adding the Fenton reagent into a reaction container filled with 2.5mg of polycarbonate micro-nano plastic (see step 2); the reaction temperature was controlled at-60 ℃ and the reaction time was 10 days.
(2) And washing the degraded product with ultrapure water, and draining to obtain the frozen micro-nano plastic degraded product. And measuring the O/C ratio of the degraded product of the frozen micro-nano plastic by using X-ray photoelectron spectroscopy (XPS), wherein the O/C ratio is shown in figure 4.
4. Normal temperature treatment (comparative reaction)
(1) Measuring 100mL of the Fenton reagent in the step 1, and adding the Fenton reagent into a reaction container filled with 2.5mg of polycarbonate micro-nano plastic (see step 2); the reaction time was 10 days.
(2) Washing the degraded product with ultrapure water, and draining to obtain the micro-nano plastic reaction product treated at normal temperature. The O/C ratio of the product after the reaction was measured using X-ray photoelectron spectroscopy (XPS), as shown in FIG. 4.
Analytical example 1
Principle analysis of freezing technique
Taking polystyrene micro-nano plastic as an example, observing polystyrene microspheres at normal temperature and polystyrene microspheres (the original particle sizes are about 600 nm) frozen to-20 ℃ by using a TEM respectively, and showing the movement tendency of the micro-nano plastic after freezing; the resulting TEM image is shown in FIG. 1.
According to the observation in figure 1, the freezing condition has the effect of enriching and concentrating the micro-nano plastic.
Analytical example 2
Comparative analysis of effects
1. Example 1 and example 2 analysis of characterization results
Scanning the polystyrene micro-nano plastic original sample, the product obtained after the reaction of the polystyrene micro-nano plastic subjected to Fenton treatment under the normal temperature condition and the product obtained after the degradation of the polystyrene micro-nano plastic subjected to Fenton treatment under the freezing condition by using an electron microscope, wherein the scanning result of the embodiment 1 is shown in figure 2, and the scanning result of the embodiment 2 is shown in figure 3.
According to the observation of fig. 2 and fig. 3, the original stable chemical state and structure of the micro-nano plastic are destroyed, so that the macro-molecules of the micro-nano plastic which are difficult to degrade are degraded, and the purpose of high-efficiency degradation is achieved.
2. Comparative analysis of degradation effect of micro-nano plastic
In the examples 1 to 9, the original micro-nano plastic sample, the product after reaction of the micro-nano plastic processed at normal temperature and the product after degradation of the micro-nano plastic processed by freezing are measured by XPS, and the degradation degree is analyzed. The degradation conditions of the micro-nano plastics in examples 1 to 9 are shown in table 1, and the XPS measurement results are shown in fig. 4.
Table 1: degradation conditions for micro-nano plastics in examples 1-9
According to the observation of fig. 4, the O/C ratios of the products of the frozen micro-nano plastic after degradation are higher than the O/C ratio of the original micro-nano plastic sample and the O/C ratio of the product of the normal temperature processed micro-nano plastic after reaction by the method for degrading the micro-nano plastic described in examples 1 to 9. And the O/C ratio of the product of the micro-nano plastic subjected to Fenton treatment under the freezing condition is basically maintained to be more than 0.10.
Therefore, the method for degrading the micro-nano plastic realizes the efficient degradation of the micro-nano plastic with low concentration in the water body. The method realizes the high-efficiency degradation of the micro-nano plastic by the low-concentration Fenton reagent; the degradation effect on micro-nano plastics is good; low cost, green chemistry, strong applicability and the like.
In summary, in the above technical solutions of the present invention, the above are only preferred embodiments of the present invention, and the technical scope of the present invention is not limited thereby, and all equivalent structural changes made by using the contents of the specification and the drawings of the present invention or other related technical fields directly/indirectly applied thereto are included in the scope of the present invention.
Claims (7)
1. A method for degrading micro-nano plastics is characterized in that the micro-nano plastics are degraded by a Fenton reagent at a temperature of-80 to-5 ℃;
wherein, in the Fenton reagent, fe 2+ And/or Fe 3+ The concentration is 0.01-120 mu mol/L, and the volume fraction of the hydrogen peroxide is 0.001-0.05%.
2. The method for degrading the micro-nano plastic according to claim 1, wherein the Fenton reagent is prepared by the following steps:
s1, providing said Fe 2+ And/or Fe 3+ To the solution of Fe 2+ And/or Fe 3+ Adding the hydrogen peroxide into the solution to obtain a mixed solution;
and S2, adjusting the pH value of the mixed solution to 2-12 to obtain the Fenton reagent.
3. The method for degrading micro-nano plastic according to claim 2, wherein in the step S1, fe 2+ And/or Fe 3+ Sources include: ferrous salts, ferric salts or mixtures of ferrous and ferric salts.
4. The method for degrading micro-nano plastic according to claim 3, wherein the ferrous salt comprises: ferrous sulfate or ferrous chloride; the iron salts include: iron sulfate, iron nitrate or iron chloride.
5. A method for degrading micro-nano plastic according to any one of claims 1 to 4, wherein the micro-nano plastic is made of materials including: one or more of polystyrene, polycarbonate, polyethylene terephthalate, nylon, polyethylene, polypropylene, and polyvinyl chloride.
6. The method for degrading the micro-nano plastic according to claim 5, wherein the particle size of the micro-nano plastic is as follows: 10-5000nm.
7. The method for degrading micro-nano plastic according to claim 1, wherein the solid-to-liquid ratio of the micro-nano plastic to the Fenton reagent is as follows: 1-5mg.
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