CN115945189A - Nano manganese-based catalyst and preparation method and application thereof - Google Patents
Nano manganese-based catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a nano manganese-based catalyst and a preparation method and application thereof. The nano manganese-based catalyst inherits the microscopic morphology and the porous structure of the precursor MOFs, and is beneficial to the generation and transfer of active oxygen, so that the nano manganese-based catalyst has excellent catalytic activity and can catalyze and purify low-concentration gaseous chlorobenzene under the condition of low temperature.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a nano manganese-based catalyst, and a preparation method and application thereof.
Background
chlorine-Containing Volatile Organic Compounds (CVOCs) are widely generated in various industrial processes such as petrochemical, paint and solvent manufacturing, and have attracted much attention because of their high toxicity, durability and difficulty in biodegradation, which are great hazards to the environment and health. Among the current numerous methods for the degradation of CVOCs, low temperature (200-550 ℃) catalytic oxidation is considered to be one of the most efficient and promising technologies.
To date, noble metals and transition metal oxides have been the primary catalysts for CVOCs catalytic oxidation reactions. Noble metal catalysts show significant activity at low loadings (0.1 to 0.5 wt%) for CVOCs. However, the formation of toxic polychlorinated by-products, rapid chlorine poisoning, and high cost limit their large-scale practical application. Recently, transition metal oxides have received much attention due to their low cost, good resistance to chlorine poisoning, and good thermal stability. There have been reports of studies on catalytic oxidation of CVOCs on Mn, ce, co, V and Fe based catalysts. Among them, manganese oxides exhibit outstanding catalytic activity for CVOCs oxidation because of Mn 3+ And Mn 4+ The redox cycle between facilitates the generation and transfer of active oxygen.
The preparation method of the transition metal oxide catalyst can be classified into two types, one of which is a one-step synthesis of the transition metal oxide catalyst, and the other of which is a two-step synthesis of the transition metal oxide by a sacrificial template method. Recently, metal organic framework Materials (MOFs) have been widely used in the fields of adsorption, advanced oxidation, photocatalysis and catalytic oxidation due to their characteristics of high specific surface area, easy surface functionalization and adjustable pore size, and the preparation of transition metal oxides using a sacrificial template method in which MOFs is used as a precursor has been effectively applied in catalytic oxidation reactions. The methods for preparing transition metal oxides using MOFs as sacrificial templates reported so far are limited to the conventional pyrolysis method, i.e. the sacrificial template is calcined at a specific temperature and in a specific gas atmosphere to obtain nanoscale metal oxide materials with excellent properties. However, the method not only has extremely high requirements on the thermal stability and the calcination conditions of the MOFs sacrificial template, but also has high pollution, high energy consumption and low efficiency in the treatment process, thereby greatly limiting the large-scale application of the MOFs sacrificial template in the synthesis of the nano oxide.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a preparation method of a nano manganese-based catalyst, which can avoid a high-pollution, high-energy-consumption and low-efficiency calcination process in the traditional technology and effectively control the micro-morphology of an oxide material.
The second aspect of the invention provides a nano manganese-based catalyst prepared by the preparation method of the nano manganese-based catalyst.
The third aspect of the invention provides an application of the nano manganese-based catalyst.
According to a first aspect of the present invention, a method for preparing a nano manganese-based catalyst is provided, which comprises the following steps:
s1: mixing manganese salt and monodentate carboxylic acid ligand, and then adding polydentate carboxylic acid ligand to perform solvothermal reaction to prepare a metal organic framework precursor;
s2: and under the oxygen-enriched atmosphere, adding the metal organic framework precursor into a solvent to perform heating reaction to prepare the nano manganese-based catalyst.
In the invention, the manganese salt and the monodentate carboxylic acid ligand are mixed in advance, then the polydentate carboxylic acid ligand is added, and the content of the polydentate carboxylic acid ligand in the metal-organic framework is reduced by utilizing the competition effect of the monodentate carboxylic acid ligand and the polydentate carboxylic acid ligand, so that the stability of the metal-organic framework is reduced, the metal-organic framework precursor can be hydrolyzed in a solvent, and the manganese oxide is generated by utilizing the dissolved oxygen in the solvent for oxidation, and no alkali source is required to be added.
In some embodiments of the invention, the molar ratio of the manganese salt, the polydentate carboxylic acid ligand and the monodentate carboxylic acid ligand is 1 (0.5-0.9) to (5-50), preferably 1 (0.5-0.8) to (10-20).
In some preferred embodiments of the present invention, the temperature of the solvothermal reaction is 100 ℃ to 200 ℃ and the time is 12h to 48h.
In some more preferred embodiments of the invention, in S1, the manganese salt is mixed with the monodentate carboxylic acid ligand in an organic solvent; preferably, the organic solvent includes at least one of N, N-dimethylformamide, ethanol and a water mixed solution.
In some more preferred embodiments of the present invention, in S2, the temperature of the temperature-increasing reaction is 30 to 150 ℃ for 6 to 24 hours.
In some more preferred embodiments of the invention, the manganese salt comprises at least one of a nitrate, acetate, sulfate, halide, or perhalate salt of manganese metal.
In some more preferred embodiments of the invention, the monodentate carboxylic acid ligand includes at least one of benzoic acid, acetic acid, heptanoic acid, octanoic acid, decanoic acid, lauric acid, myristic acid, and palmitic acid or stearic acid.
In some more preferred embodiments of the present invention, the multidentate carboxylic acid ligand includes 1,3,5-trimesic acid, terephthalic acid, or both.
In some more preferred embodiments of the present invention, in S2, the solvent comprises water or a mixed solvent of water and at least one of methanol, ethanol, propanol, isopropanol, diethyl ether, acetone, 1,4-dioxane, tetrahydrofuran, dimethyl sulfoxide; preferably, the volume ratio of water in the mixed solvent is 50-90%.
In some more preferred embodiments of the present invention, in S2, the oxygen-rich atmosphere comprises at least one of introducing oxygen, adding a peroxygen source; preferably, the oxygen-rich atmosphere comprises bringing the dissolved oxygen concentration in the solvent to a saturated dissolved oxygen concentration at the reaction temperature.
According to a second aspect of the invention, the invention provides a nano manganese-based catalyst prepared by the preparation method of the nano manganese-based catalyst.
According to a third aspect of the invention, the application of the nano manganese-based catalyst in chlorobenzene catalysis is provided.
In some embodiments of the invention, the chlorobenzene comprises gaseous chlorobenzene.
In some preferred embodiments of the present invention, the chlorobenzene comprises a low concentration of chlorobenzene; preferably, the concentration of chlorobenzene is between 50ppm and 100ppm.
In some preferred embodiments of the invention, the catalysis is carried out at a temperature of from 120 ℃ to 250 ℃.
The invention has the beneficial effects that:
1) The manganese-based metal organic framework is used as a precursor, and the content of the polydentate carboxylic acid ligand in the metal organic framework is reduced by utilizing the competition effect of the monodentate carboxylic acid ligand and the polydentate carboxylic acid ligand, so that the stability of the metal organic framework is reduced, the metal organic framework precursor can be hydrolyzed in a solvent, and the manganese oxide is generated by utilizing the dissolved oxygen in the solvent and oxidizing without adding an alkali source.
2) The catalyst prepared by the invention avoids the problems of MOFs structure collapse and particle agglomeration in the traditional pyrolysis method, and meanwhile, the ligand is not decomposed and can be recycled, so that the preparation cost is saved, and the catalyst is beneficial to large-scale production and application.
3) The nano manganese-based catalyst inherits the microscopic morphology and the porous structure of the precursor MOFs, is beneficial to the generation and transfer of active oxygen, has excellent catalytic activity and can be used for catalytically purifying low-concentration gaseous chlorobenzene at low temperature (less than 250 ℃).
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is an XRD pattern of MOF precursor, product catalyst and product catalysts of comparative examples 1-3 during preparation of example 1 of the invention.
FIG. 2 is a TEM image of MOF precursors and product catalysts during preparation of example 1 of the present invention; wherein (a) is a TEM image of the MOF precursor in example 1; (b) is a TEM image of the catalyst in example 1.
FIG. 3 is a TEM image of MOF precursors and product catalysts in the preparation process of comparative example 3; wherein (a) is a TEM image of the MOF precursor in comparative example 3; (b) is a TEM image of the catalyst in comparative example 3.
Detailed Description
The idea of the invention and the resulting technical effects will be clearly and completely described below in connection with the embodiments, so that the objects, features and effects of the invention can be fully understood. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and other embodiments obtained by those skilled in the art without inventive efforts are within the protection scope of the present invention based on the embodiments of the present invention.
Example 1
The embodiment prepares a nano manganese-based catalyst, and the specific process is as follows:
0.5mmol of manganese nitrate and 5mmol of benzoic acid are dissolved in 20mLN and N-dimethylformamide, stirred for 0.5h at room temperature, then 0.25mmol of 1,3, 5-trimesic acid is added, after the uniform dissolution and mixing, the reaction is carried out for 24h at 120 ℃, and white powder is obtained after filtration, washing and drying. Oxygen (50 mL/min) is introduced into 200mL of water for 2h, 1g of the prepared white powder is dispersed in the water, the mixture is hydrolyzed at 30 ℃ for 24h under the condition of stirring, and the nano manganese-based catalyst is obtained by filtering, washing and drying.
Example 2
The embodiment prepares the nano manganese-based catalyst, and the specific process comprises the following steps:
0.5mmol of manganese chloride and 10mmol of acetic acid are dissolved in 20mLN and N-dimethylformamide, stirred for 0.5h at room temperature, then 0.4mmol of 1,3, 5-trimesic acid is added, after the uniform dissolution and mixing, the reaction is carried out for 24h at 130 ℃, and white powder is obtained after filtration, washing and drying. Introducing oxygen (50 mL/min) into a mixed solvent of 180mL of water and 20mL of acetone for 2h, dispersing 1g of the prepared white powder in the mixed solvent, hydrolyzing at 120 ℃ for 8h under the condition of stirring, filtering, washing and drying to obtain the nano manganese-based catalyst.
Example 3
The embodiment prepares the nano manganese-based catalyst, and the specific process comprises the following steps:
dissolving 0.5mmol of manganese acetate and 10mmol of heptanoic acid in 20mLN and N-dimethylformamide, stirring at room temperature for 0.5h, adding 0.3mmol of 1,3 and 5-trimesic acid, reacting at 135 ℃ for 36h after uniformly dissolving and mixing, filtering, washing and drying to obtain white powder. Introducing oxygen (50 mL/min) into a mixed solvent of 160mL of water and 40mL of tetrahydrofuran for 2h, dispersing 1g of the prepared white powder in the mixed solvent, hydrolyzing at 150 ℃ for 6h under the condition of stirring, filtering, washing and drying to obtain the nano manganese-based catalyst.
Example 4
The embodiment prepares the nano manganese-based catalyst, and the specific process comprises the following steps:
dissolving 0.5mmol of manganese sulfate and 10mmol of octanoic acid in 20mLN and N-dimethylformamide, stirring at room temperature for 0.5h, adding 0.35mmol of 1,3 and 5-trimesic acid, reacting at 120 ℃ for 48h after dissolving and mixing uniformly, filtering, washing and drying to obtain white powder. Introducing oxygen (50 mL/min) into a mixed solvent of 150mL of water and 50mL of dimethyl sulfoxide for 2h, dispersing 1g of the prepared white powder in the mixed solvent, hydrolyzing at 80 ℃ for 12h under the condition of stirring, filtering, washing and drying to obtain the nano manganese-based catalyst.
Example 5
The embodiment prepares the nano manganese-based catalyst, and the specific process comprises the following steps:
dissolving 0.5mmol of manganese nitrate and 7.5mmol of capric acid in 20mLN and N-dimethylformamide, stirring at room temperature for 0.5h, adding 0.25mmol of 1,3 and 5-trimesic acid, reacting at 150 ℃ for 24h after uniformly dissolving and mixing, filtering, washing and drying to obtain white powder. Introducing oxygen (50 mL/min) into a mixed solvent of 140mL of water and 60mL1, 4-dioxane for 2h, dispersing 1g of the prepared white powder in the mixed solvent, hydrolyzing at 100 ℃ for 10h under the condition of stirring, filtering, washing and drying to obtain the nano manganese-based catalyst.
Example 6
The embodiment prepares the nano manganese-based catalyst, and the specific process comprises the following steps:
dissolving 0.5mmol of manganese nitrate and 7.5mmol of lauric acid in 20mLN and N-dimethylformamide, stirring at room temperature for 0.5h, then adding 0.375mmol of 1,3, 5-trimesic acid, reacting at 120 ℃ for 48h after uniformly dissolving and mixing, filtering, washing and drying to obtain white powder. Introducing oxygen (50 mL/min) into a mixed solvent of 100mL of water and 100mL of ethanol for 2h, dispersing 1g of the prepared white powder in the mixed solvent, hydrolyzing at 60 ℃ for 20h under the condition of stirring, filtering, washing and drying to obtain the nano manganese-based catalyst.
Example 7
The embodiment prepares the nano manganese-based catalyst, and the specific process comprises the following steps:
dissolving 0.5mmol of manganese nitrate and 5mmol of palmitic acid in 20mLN and N-dimethylformamide, stirring at room temperature for 0.5h, then adding 0.325mmol of 1,3, 5-trimesic acid, reacting at 160 ℃ for 24h after uniformly dissolving and mixing, filtering, washing and drying to obtain white powder. Introducing oxygen (50 mL/min) into a mixed solvent of 125mL of water and 75mL of isopropanol for 2h, dispersing 1g of the prepared white powder in the mixed solvent, hydrolyzing at 75 ℃ for 15h under the condition of stirring, filtering, washing and drying to obtain the manganese oxide catalyst.
Comparative example 1
The comparative example prepared a catalyst, the specific process was:
0.5mmol of manganese nitrate and 5mmol of benzoic acid are dissolved in 20mLN and N-dimethylformamide, stirred for 0.5h at room temperature, then 0.25mmol of 1,3, 5-trimesic acid is added, after the uniform dissolution and mixing, the reaction is carried out for 24h at 120 ℃, and white powder is obtained after filtration, washing and drying. Introducing nitrogen (50 mL/min) into 200mL of water for 2h, dispersing 1g of powder in the water, stirring the mixture for 24h at 30 ℃ under the protection of nitrogen, filtering, washing and drying to obtain the catalyst.
Comparative example 2
The comparative example prepared a catalyst, the specific process was:
dissolving 0.5mmol of manganese nitrate and 5mmol of benzoic acid in 20mLN and N-dimethylformamide, stirring at room temperature for 0.5h, adding 0.25mmol of 1,3 and 5-trimesic acid, reacting at 120 ℃ for 24h after uniformly dissolving and mixing, filtering, washing and drying to obtain white powder. 1g of the powder is put under nitrogen atmosphere, and the temperature is raised to 700 ℃ at the heating rate of 2 ℃/min and kept for 2h to obtain the catalyst.
Comparative example 3
The comparative example prepared a catalyst, the specific process was:
dissolving 0.5mmol of manganese nitrate and 0.5mmol of 1,3, 5-trimesic acid in 20mLN and N-dimethylformamide, stirring at room temperature for 0.5h, reacting at 120 ℃ for 24h after dissolving and mixing uniformly, filtering, washing and drying to obtain white powder. Oxygen (50 mL/min) is introduced into 200mL of water for 2h, 1g of powder is dispersed in the water, the mixture is hydrolyzed for 24h at 30 ℃ under the condition of stirring, and the catalyst is obtained by filtering, washing and drying.
Test example 1
In this experimental example, XRD and TEM tests were performed on the MOF precursors and the prepared catalysts in the preparation processes of the examples and comparative examples.
FIG. 1 is an XRD pattern of MOF precursor, product catalyst and product catalysts of comparative examples 1-3 during preparation of example 1 of the invention. As can be seen from FIG. 1, the diffraction peaks corresponding to the nano-manganese-based catalyst prepared in example 1 are concentrated at 28.9, 32.4 and 36.1 degrees, which are attributed to Mn 3 O 4 (PDF standard card number: 75-1560) that the active component of the nano manganese-based catalyst prepared by the invention is Mn 3 O 4 . The diffraction peak corresponding to the catalyst prepared in comparative example 1 did not appear to be attributed to Mn 3 O 4 The diffraction peak of (a) is close to the peak pattern of the MOF precursor in example 1, indicating that in the absence of oxygen, the MOF precursor cannot be hydrolyzed sufficiently to prepare the nano manganese-based catalyst. Catalyst prepared in comparative example 2 except containing Mn 3 O 4 In addition to the diffraction peaks of (B), characteristic diffraction peaks ascribed to MnO (PDF standard card number: 89-4835) also appeared at 34.9 °, 40.6 ° and 58.7 °, indicating that Mn was formed in comparative example 2 3 O 4 And MnO, mainly due to the lack of oxygen produced by calcination in an inert atmosphere as in comparative example 2. The catalyst prepared in comparative example 3 was similar to that of comparative example 1, and no Mn ascribed thereto was observed 3 O 4 The diffraction peak of (a), is similar to the peak pattern of the MOF precursor in example 1, indicating that the absence of monodentate ligands can improve the stability of the MOF precursor, resulting in inability to hydrolyze under mild conditions to prepare a manganese oxide catalyst.
FIG. 2 is a TEM image of MOF precursor and product catalyst in the preparation process of example 1, and FIG. 2 (a) is a TEM image of MOF precursor in example 1; in the figure, 2 (b) is a TEM image of the catalyst in example 1. From fig. 2 (a) it can be seen that the MOF precursor exhibits a typical rod-like structure, but a pronounced pore structure occurs due to the heterogeneous nature of the addition of monodentate carboxylic acid ligands. After hydrolysis with dissolved oxygen, the catalysis prepared in example 1 can be seen from FIG. 2 (b)The agent still inherits the rod-like structure of the MOF precursor, and Mn 3 O 4 The nanoparticles are uniformly distributed therein, and no significant agglomeration occurs.
FIG. 3 is a TEM image of MOF precursor and product catalyst in the preparation process of comparative example 3 of the present invention, wherein 3 (a) is a TEM image of MOF precursor in comparative example 3; in the figure, 3 (b) is a TEM image of the catalyst in comparative example 3. As can be seen by comparison with figure 2, in comparative example 3 no significant pore structure appeared in the MOF precursor due to the absence of monodentate carboxylic acid ligands, but a homogeneous solid structure. After the oxygen-dissolved water treatment, as can be seen from FIG. 3 (b), the catalyst prepared in comparative example 3 still maintains the structure of the MOF precursor, and Mn does not appear 3 O 4 The nano particles show that the precursor has better stability and is not hydrolyzed.
Test example 2
This test example shows the catalysts and commercial Mn obtained in the examples and comparative examples 3 O 4 The performance of the product for degrading and catalyzing chlorobenzene is tested, and the specific process is as follows:
and (3) testing conditions: the initial concentration of chlorobenzene as raw material gas is 50ppm, the total flow rate of gas is 20mL/min, the size of the catalyst is 40-60 meshes, the loading amount is 100mg, and the space velocity is 12000 mL/(g.h).
The test method comprises the following steps: the raw material gas passes through a quartz tube reactor filled with a catalyst, the quartz tube reactor is placed in a temperature control furnace to control the reaction temperature, and after the reaction gas reacts for 30min at a certain temperature, the gas passes through a gas chromatograph to detect the concentration of outlet chlorobenzene on line. The conversion rate of the catalyst to chlorobenzene is calculated to express the catalytic activity of the catalyst to chlorobenzene.
Catalysts prepared in examples 1 to 7 and comparative examples 1 to 3 and commercial Mn 3 O 4 Product Performance Single test results, as shown in Table 1, wherein T 50 、T 90 The reaction temperatures required for 50% and 90% conversion, respectively.
TABLE 1 Chlorobenzene catalytic Oxidation Performance test results for different catalysts
| Catalyst and process for preparing same | T 50 (℃) | T 90 (℃) |
| Example 1 | 160 | 198 |
| Example 2 | 165 | 200 |
| Example 3 | 171 | 212 |
| Example 4 | 168 | 207 |
| Example 5 | 175 | 215 |
| Example 6 | 175 | 217 |
| Example 7 | 168 | 209 |
| Comparative example 1 | / | / |
| Comparative example 2 | 194 | 235 |
| Comparative example 3 | / | / |
| Commercial Mn 3 O 4 | 229 | 256 |
As can be seen from Table 1: the manganese oxide catalysts prepared by the preparation method of the present invention (i.e., the catalysts of examples 1 to 7) had better reactivity than the manganese-based catalysts and commercial Mn of comparative examples 1 to 3 under the above-mentioned test conditions 3 O 4 A catalyst.
Mn prepared in example 1 3 O 4 The catalyst can realize 90 percent conversion of p-chlorobenzene at the reaction temperature of 198 ℃, while the manganese-based catalyst prepared in the comparative example 1 can not even reach 50 percent conversion, and the conversion rate of p-chlorobenzene only reaches 32 percent at most. The reason is that in the hydrolysis process, due to the lack of oxygen in the solvent and the environment, the hydrolysis of the MOF precursor is influenced, so that manganese oxide cannot be formed, and the chlorobenzene is converted mainly by utilizing the adsorption effect of the unhydrolyzed MOF precursor on the chlorobenzene, so that the chlorobenzene cannot be converted by increasing the reaction temperature, but the chlorobenzene desorption balance is influenced, so that the chlorobenzene is desorbed. In analogy to comparative example 3, the failure to form oxides of manganese was mainly due to the absence of monodentate ligands, resulting in MOF precursors that are stable under mild conditions and cannot be hydrolyzed to form oxides of manganese. T of manganese-based catalyst prepared in comparative example 2 90 An increase of 37 ℃ is required compared to example 1. This is mainly due to the inert atmosphereThe lack of oxygen in the manganese-based catalyst prepared by calcination results in insufficient oxidation of manganese. While commercial Mn 3 O 4 T of catalyst 90 An increase of 58 ℃ is required compared to example 1, mainly because of commercial Mn 3 O 4 MOF-free Structure of the catalyst vs Mn 3 O 4 The dispersion of the nano particles leads to the agglomeration of the particles, so that the active sites are greatly reduced, and the catalytic activity is reduced.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the embodiments, and various changes can be made without departing from the gist of the present invention within the knowledge of those skilled in the art. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. A preparation method of a nano manganese-based catalyst is characterized by comprising the following steps: the method comprises the following steps:
s1: mixing manganese salt and monodentate carboxylic acid ligand, and then adding polydentate carboxylic acid ligand to perform solvothermal reaction to prepare a metal organic framework precursor;
s2: and under the oxygen-enriched atmosphere, adding the metal organic framework precursor into a solvent to perform heating reaction to prepare the nano manganese-based catalyst.
2. The method for preparing a nano manganese-based catalyst according to claim 1, characterized in that: the molar ratio of the manganese salt to the polydentate carboxylic acid ligand to the monodentate carboxylic acid ligand is 1 (0.5-0.8) to 10-20.
3. The method for preparing a nano manganese-based catalyst according to claim 1, characterized in that: the monodentate carboxylic acid ligand includes at least one of benzoic acid, acetic acid, heptanoic acid, octanoic acid, decanoic acid, lauric acid, myristic acid, and palmitic acid or stearic acid.
4. The method for preparing a nano manganese-based catalyst according to claim 1, characterized in that: the polydentate carboxylic acid ligand comprises 1,3,5-trimesic acid and at least one of terephthalic acid.
5. The method for preparing a nano manganese-based catalyst according to claim 1, characterized in that: in S2, the solvent comprises water or a mixed solvent of water and at least one of methanol, ethanol, propanol, isopropanol, diethyl ether, acetone, 1,4-dioxane, tetrahydrofuran and dimethyl sulfoxide.
6. The method for preparing a nano manganese-based catalyst according to claim 1, characterized in that: in S2, the temperature of the temperature rise reaction is 30-150 ℃, and the time is 6-24 h.
7. A nano manganese-based catalyst prepared by the method for preparing a nano manganese-based catalyst according to any one of claims 1 to 6.
8. Use of the nano-manganese-based catalyst of claim 7 in the catalysis of chlorobenzene.
9. Use according to claim 8, characterized in that: the catalysis is carried out at 120-250 ℃.
10. Use according to claim 8, characterized in that: the concentration of the chlorobenzene is 50 ppm-100 ppm.
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