MILLIMETER-SCALE PEROXYMONOSULFATE ACTIVATOR ZSM-5-(C@Fe) AND PREPARATION METHOD AND APPLICATION THEREOF

Abstract

A millimeter-scale peroxymonosulfate activator ZSM-5-(C@Fe) and a preparation method and an application thereof are provided. According to the method, a PMS activator ZSM-5-(C@Fe) with a millimeter-scale stable structure is synthesized in the following steps: (1) preprocessing a ZSM-5 by a carboxylation method to obtain a ZSM-5-COOH; (2) synthesizing a ferrous metal organic framework material by a thermal method to obtain a precursor Fe (II)-MOF-74; (3) dispersing the ZSM-5-COOH in the step (1) and an ethyldiol methacrylate in an acetonitrile, and mixing evenly to obtain a mixed solution; and adding the precursor Fe(II)-MOF-74 in the step (2) into the mixed solution, carrying out a stirring reaction under an action of an initiator, filtering to obtain a precipitate, washing, and drying in vacuum to obtain ZSM-5-MOFs; and (4) in a nitrogen atmosphere, heating the ZSM-5-MOFs in the step (3) to carry out high-temperature pyrolysis to obtain the millimeter-scale peroxymonosulfate activator ZSM-5-(C@Fe).

Claims

1. A preparation method of a millimeter-scale peroxymonosulfate activator ZSM-5-(C@Fe), comprising the following steps: (1) preprocessing a ZSM-5 by a carboxylation method to obtain a ZSM-5-COOH; (2) synthesizing a ferrous metal organic framework material by a thermal method to obtain a precursor Fe (II)-MOF-74; (3) dispersing the ZSM-5-COOH in the step (1) and an ethyldiol methacrylate in an acetonitrile, and mixing evenly to obtain a mixed solution; and adding the precursor Fe(II)-MOF-74 in the step (2) into the mixed solution, carrying out a stirring reaction under an action of an initiator, filtering to obtain a precipitate, washing, and drying in vacuum to obtain ZSM-5-MOFs; and (4) in a nitrogen atmosphere, heating the ZSM-5-MOFs in the step (3) to carry out high-temperature pyrolysis to obtain the millimeter-scale peroxymonosulfate activator ZSM-5-(C@Fe).

2. The preparation method of the millimeter-scale peroxymonosulfate activator ZSM-5-(C@Fe) according to claim 1, wherein a mass ratio of the ZSM-5-COOH to the precursor Fe(II)-MOF-74 in the step (3) is 10:1 to 10:2.

3. The preparation method of the millimeter-scale peroxymonosulfate activator ZSM-5-(C@Fe) according to claim 1, wherein a mass-volume ratio of the ZSM-5-COOH to the acetonitrile in the step (3) is (5 to 15):100 g/mL.

4. The preparation method of the millimeter-scale peroxymonosulfate activator ZSM-5-(C@Fe) according to claim 1, wherein a molar volume ratio of the ethyldiol methacrylate to the acetonitrile in the step (3) is (25 to 75):100 mmol/mL.

5. The preparation method of the millimeter-scale peroxymonosulfate activator ZSM-5-(C@Fe) according to claim 1, wherein the stirring reaction in the step (3) is carried out at 40° C. to 80° C. for 20 hours to 28 hours; and the initiator is azobisisobutyronitrile.

6. The preparation method of the millimeter-scale peroxymonosulfate activator ZSM-5-(C@Fe) according to claim 1, wherein the drying in vacuum in the step (3) is carried out at 50° C. to 80° C. for 10 hours to 12 hours.

7. The preparation method of the millimeter-scale peroxymonosulfate activator ZSM-5-(C@Fe) according to claim 1, wherein the high-temperature pyrolysis in the step (4) is carried out at 400° C. to 600° C. for 1 hour to 3 hours.

8. A millimeter-scale peroxymonosulfate activator ZSM-5-(C@Fe) prepared by the preparation method according to claim 1.

9. A method of applying the millimeter-scale peroxymonosulfate activator ZSM-5-(C@Fe) according to claim 8 in treating emerging contaminants (ECs) in wastewater, comprising the following steps: adding the millimeter peroxymonosulfate activator ZSM-5-(C@Fe) and a peroxymonosulfate into the wastewater containing the ECs, and then performing a catalytic activation reaction in a shaking table to obtain the treated wastewater.

10. The method of applying the millimeter-scale peroxymonosulfate activator ZSM-5-(C@Fe) in treating the ECs in the wastewater according to claim 9, wherein a molar ratio of the peroxymonosulfate to the ECs in the wastewater is 10:1 to 50:1; an adding amount of the millimeter peroxymonosulfate activator ZSM-5-(C@Fe) is 1 g.Math.L.sup.−1 to 5 g.Math.L.sup.−1; the ECs are more than one of tetrabromobisphenol A, sulfamethoxazole, trichlorophenol, and ciprofloxacin; the shaking table has a rotating speed of 50 rpm to 200 rpm, and the catalytic activation reaction lasts for 10 minutes to 30 minutes.

11. A millimeter-scale peroxymonosulfate activator ZSM-5-(C@Fe) prepared by the preparation method according to claim 2.

12. A millimeter-scale peroxymonosulfate activator ZSM-5-(C@Fe) prepared by the preparation method according to claim 3.

13. A millimeter-scale peroxymonosulfate activator ZSM-5-(C@Fe) prepared by the preparation method according to claim 4.

14. A millimeter-scale peroxymonosulfate activator ZSM-5-(C@Fe) prepared by the preparation method according to claim 5.

15. A millimeter-scale peroxymonosulfate activator ZSM-5-(C@Fe) prepared by the preparation method according to claim 6.

16. A millimeter-scale peroxymonosulfate activator ZSM-5-(C@Fe) prepared by the preparation method according to claim 7.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0038] FIG. 1 is an X-ray crystallogram (XRD) of a ZSM-5-(C@Fe) in the Embodiment 1; and

[0039] FIG. 2 is a scanning electron micrograph (SEM) of the ZSM-5-(C@Fe) in the Embodiment 1.

DETAILED DESCRIPTION

[0040] The specific implementation of the present invention is further described with reference to the embodiments, but the implementation and the protection of the present invention are not limited hereto. It should be noted that if there is any process that is not specifically described in detail hereinafter, it may be realized or understood by those skilled in the art with reference to the prior art. If the manufacturer of the reagent or the instrument used is not indicated, the reagent or the instrument is regarded as a conventional product capable of being purchased from the market.

Embodiment 1

[0041] In the embodiment, a ZSM-5-(C@Fe) prepared with a good ability to degrade emerging contaminants was investigated.

[0042] (1) Preparation of the ZSM-5-(C@Fe): 10 g of ZSM-5, 150 mmol of 3-aminopropyltriethoxysilane, and 150 mmol of maleic anhydride were evenly dispersed in 100 mL of N,N-dimethylformamide, and stirred at a room temperature for 24 hours; and then, a granular sample was washed with methanol, and dried at 50° C. for 12 hours to obtain a precursor ZSM-5-COOH. Terephthalic acid (1.065 g) and FeCl.sub.2.4H.sub.2O (2.65 g) were put into a 500 ml three-necked bottle, 250 ml of N, N-dimethylformamide was added to dissolve the mixture, then 30 ml of methanol was added, and 8 ml of hydrofluoric acid was dropwise added to enable a solution to be pale green, then heated to 140° C., and reacted for 24 hours to obtain a ferrous MOFs precursor (Fe(II)-MOF-74). 10 g of ZSM-5-COOH and 50 mmol of ethyldiol methacrylate were dispersed in 100 mL of acetonitrile to obtain a mixed solution. Then, 1 g of Fe(II)-MOF-74 and 20 mg of azobisisobutyronitrile were put into the mixed solution, and stirred at 60° C. for 24 hours. The granular sample was filtered out, washed with methanol, and then dried in a vacuum furnace at 50° C. for 12 hours to obtain white precursors ZSM-5-MOFs. Then, the ZSM-5-MOFs were subjected to high-temperature pyrolysis in a tube furnace at 500° C. for 2 hours in a nitrogen atmosphere, and the millimeter-scale PMS activator ZSM-5-(C@Fe) was finally obtained. FIG. 1 is an X-ray crystallogram (XRD) of the ZSM-5-(C@Fe) in the Embodiment 1, and the ZSM-5-(C@Fe) is found to have characteristic peaks of two crystals of ZSM-5 and Fe. FIG. 2 is a scanning electron micrograph (SEM) of the ZSM-5-(C@Fe) in the Embodiment 1, and a surface of a millimeter sphere of the ZSM-5-(C@Fe) is found to be distributed with micron-scale rod structures.

[0043] (2) A ciprofloxacin solution with a concentration of 0.036 mmol.Math.L.sup.−1 was prepared as ECs for later use.

[0044] (3) A conical flask was used as a reactor, 100 mL of ciprofloxacin solution (with a concentration of 0.036 mol.Math.L.sup.−1), 0.036 mmol of PMS, and 0.05 g of ZSM-5 were respectively added into a reactor 1, and the reactor was put into a shaking table at 180 rpm for a degradation reaction at a room temperature (25° C.).

[0045] (4) 0.1 g of ZSM-5-COOH was added into a reactor 2, without adding the ZSM-5, and other conditions were the same as those in the step (3).

[0046] (5) 0.1 g of ZSM-5-MOFs were added into a reactor 3, without adding the ZSM-5, and other conditions were the same as those in the step (3).

[0047] (6) 0.1 g of ZSM-5-(C@Fe) was added into a reactor 4, without adding the ZSM-5, and other conditions were the same as those in the step (3).

[0048] Removal rates of ciprofloxacin under different catalysts are shown in Table 1.

TABLE-US-00001 TABLE 1 Removal Removal Removal Removal rate % rate % rate % Time rate % (ZSM-5- (ZSM-5- (ZSM-5- (min) (ZSM-5) COOH) MOFs) (C@Fe)) 0 0 0 0 0 2 8.86 7.59 14.78 23.78 4 16.56 17.86 27.56 40.56 6 21.03 20.99 39.78 54.89 10 24.56 23.89 44.86 67.89 15 25.89 24.99 49.86 78.56 20 25.85 25.12 53.78 89.78 30 25.78 25.18 57.79 100

[0049] It can be seen from Table 1 that: catalytic activation of the PMS with the ZSM-5-(C@Fe) to degrade the ciprofloxacin has a significant removal effect, because an activation site in the ZSM-5-(C@Fe) may generate both a free radical degradation pathway based on a sulfate anion radical and a non-free-radical degradation pathway based on singlet oxygen, so that an activation efficiency and a degradation rate of the emerging contaminants are improved.

Embodiment 2

[0050] In the embodiment, effects of adding amounts of a ZSM-5-(C@Fe) on catalytic activation to degrade a ciprofloxacin were compared.

[0051] (1) A preparation method of the ZSM-5-(C@Fe) was the same as the step (1) in the Embodiment 1.

[0052] (2) 0.036 mmol.Math.L.sup.−1 ciprofloxacin solution was prepared for later use.

[0053] (3) A conical flask was used as a reactor, 0.036 mmol of PMS and 100 mL of ciprofloxacin solution with a concentration of 0.036 mmol.Math.L.sup.−1 were added into a reactor 1, 0.1 g of ZSM-5-(C@Fe) was added into the reactor at the same time, the conical flask was put into a shaking table at 180 rpm for reaction at a room temperature (25° C.), and spot sampling analysis was carried out.

[0054] (4) An adding amount of the ZSM-5-(C@Fe) in a reactor 2 became 0.2 g, and other conditions were the same as those in the (3).

[0055] (5) An adding amount of the ZSM-5-(C@Fe) in a reactor 3 became 0.3 g, and other conditions were the same as those in the (3).

[0056] (6) An adding amount of the ZSM-5-(C@Fe) in a reactor 4 became 0.4 g, and other conditions were the same as those in the (3).

[0057] (7) An adding amount of the ZSM-5-(C@Fe) in a reactor 5 became 0.5 g, and other conditions were the same as those in the (3).

[0058] Removal rates of the ciprofloxacin under different adding amounts of the ZSM-5-(C@Fe) are shown in Table 2.

TABLE-US-00002 TABLE 2 Removal Removal Removal Removal Removal Time rate % rate % rate % rate % rate % (min) (0.1) (0.2) (0.3) (0.4) (0.5) 0 0 0 0 0 0 2 29.89 32.31 33.68 34.22 36.56 4 50.56 54.78 56.78 59.11 61.89 6 66.35 72.56 75.89 81.53 82.45 10 82.35 87.56 90.56 94.78 94.89 15 91.46 97.56 100 100 100 20 100 100 100 100 100 30 100 100 100 100 100

[0059] It can be seen from Table 2 that: at 30 minutes, with an increasing adding amount of the ZSM-5-(C@Fe), a degradation efficiency is increased first, and then shows a steady trend when the adding amount of the catalyst reaches 0.4 g. Considering a reaction efficiency and a cost, the adding amount of the ZSM-5-(C@Fe) of 4 g.Math.L.sup.−1 is a best choice.

Embodiment 3

[0060] In the embodiment, effects of different molar ratios of a PMS to a ciprofloxacin on a catalytic activation reaction with a ZSM-5-(C@Fe) were compared.

[0061] (1) A preparation method of the ZSM-5-(C@Fe) was the same as the step (1) in the Embodiment 1.

[0062] (2) 0.036 mmol.Math.L.sup.−1 ciprofloxacin solution was prepared for later use.

[0063] (3) A conical flask was used as a reactor, 0.036 mmol of PMS and 100 mL of ciprofloxacin solution with a concentration of 0.036 mmol.Math.L.sup.−1 were added into a reactor 1, 0.4 g of ZSM-5-(C@Fe) was added into the reactor at the same time, the conical flask was put into a shaking table at 180 rpm for reaction at a room temperature (25° C.), and spot sampling analysis was carried out.

[0064] (4) An adding amount of the PMS in a reactor 2 became 0.072 mmol, and other conditions were the same as those in the (3).

[0065] (5) An adding amount of the PMS in a reactor 3 became 0.108 mmol, and other conditions were the same as those in the (3).

[0066] (6) An adding amount of the PMS in a reactor 4 became 0.144 mmol, and other conditions were the same as those in the (3).

[0067] (7) An adding amount of the PMS in a reactor 5 became 0.180 mmol, and other conditions were the same as those in the (3).

[0068] Removal rates of the ciprofloxacin degraded by catalytically activating the PMS with the ZSM-5-(C@Fe) under different molar ratios of the PMS to the ciprofloxacin are shown in Table 3.

TABLE-US-00003 TABLE 3 Removal Removal Removal Removal Removal Time rate % rate % rate % rate % rate % (min) (10:1) (20:1) (30:1) (40:1) (50:1) 0 0 0 0 0 0 2 26 30 32.22 34.22 35.56 4 54 54 56.11 59.11 60.89 6 75 77 79.53 81.53 81.45 10 89 92 92.78 94.78 94.82 15 98.8 100 100 100 100 20 100 100 100 100 100 30 100 100 100 100 100

[0069] It can be seen from table 3 that: with increase of a ratio of n PMS/n ciprofloxacin, the removal rate of the ciprofloxacin is increased first and then decreased. When the ratio exceeds 40:1 (molar ratio), the removal rate is increased slowly. Considering a reaction efficiency and a cost, n PMS/n ciprofloxacin=40:1 is a best choice.

Embodiment 4

[0070] In the embodiment, effects of degradation of four ECs by activating a PMS with a ZSM-5-(C@Fe) were investigated.

[0071] (1) A preparation method of the ZSM-5-(C@Fe) was the same as the step (1) in the Embodiment 1.

[0072] (2) A tetrabromobisphenol A solution, a sulfamethoxazole solution, a trichlorophenol solution, and a ciprofloxacin solution with a concentration of 0.036 mmol.Math.L.sup.−1 were prepared as ECs for later use.

[0073] (3) A conical flask was used as a reactor, 0.144 mmol of PMS and 100 mL of ciprofloxacin solution with a concentration of 0.036 mmol.Math.L.sup.−1 were added into a reactor 1, 0.4 g of ZSM-5-(C@Fe) was added into the reactor at the same time, the conical flask was put into a shaking table at 180 rpm for reaction at a room temperature (25° C.), and spot sampling analysis was carried out.

[0074] (4) 100 mL of 0.036 mmol.Math.L.sup.−1 tetrabromobisphenol A solution was added into a reactor 2 without adding the ciprofloxacin solution. Other conditions were the same as those in the (3).

[0075] (5) 100 mL of 0.036 mmol.Math.L.sup.−1 sulfamethoxazole solution was added into a reactor 3 without adding the ciprofloxacin solution. Other conditions were the same as those in the (3).

[0076] (6) 100 mL of 0.036 mmol.Math.L.sup.−1 trichlorophenol solution was added into a reactor 4 without adding the ciprofloxacin solution. Other conditions were the same as those in the (3).

[0077] Effects of degradation of four ECs by activating the PMS with the ZSM-5-(C@Fe) are shown in FIG. 4.

TABLE-US-00004 TABLE 4 Removal Removal Removal Removal rate % rate % rate % rate % Time (Cipro- (Tetrabromo- (Sulfameth- (Trichloro- (min) floxacin) bisphenol A) oxazole) phenol) 0 0 0 0 0 2 34.22 32.31 33.68 34.22 4 59.11 54.78 56.78 59.11 6 81.53 72.56 75.89 81.53 10 94.78 87.56 90.56 94.78 15 100 100 100 100 20 100 100 100 100 30 100 100 100 100

[0078] It can be seen from Table 4 that: at 30 minutes, good removal effects of multiple ECs degraded by catalytically activating the PMS with the ZSM-5-(C@Fe) are realized.

Embodiment 5

[0079] In the embodiment, recycling of a degradation reaction of a tetrabromobisphenol A by catalytically activating a PMS with a ZSM-5-(C@Fe) was investigated.

[0080] (1) A preparation method of the ZSM-5-(C@Fe) was the same as the step (1) in the Embodiment 1.

[0081] (2) 0.036 mmol.Math.L.sup.−1 ciprofloxacin solution was prepared for later use.

[0082] (3) A conical flask was used as a reactor, 0.144 mmol of PMS and 100 mL of ciprofloxacin solution with a concentration of 0.036 mmol.Math.L.sup.−1 were added into a reactor 1, 0.4 g of ZSM-5-(C@Fe) was added into the reactor at the same time, the conical flask was put into a shaking table at 180 rpm for reaction at a room temperature (25° C.), and spot sampling analysis was carried out.

[0083] (4) After the step (3) was finished, the ZSM-5-(C@Fe) in a reactor 1 was recovered, the degradation reaction was continued, and conditions were the same as those in the (3).

[0084] (5) After the step (4) was finished, the ZSM-5-(C@Fe) in the reactor 1 was recovered, the degradation reaction was continued, and conditions were the same as those in the (3).

[0085] (6) After the step (5) was finished, the ZSM-5-(C@Fe) in the reactor 1 was recovered, the degradation reaction was continued, and conditions were the same as those in the (3).

[0086] (7) After the step (6) was finished, the ZSM-5-(C@Fe) in the reactor 1 was recovered, the degradation reaction was continued, and conditions were the same as those in the (3).

[0087] Removal rates of the ciprofloxacin obtained by five processes are shown in Table 5.

TABLE-US-00005 TABLE 5 Removal Removal Removal Removal Removal rate % rate % rate % Time rate % rate % (Three (Four (Five (min) (Once) (Twice) times) times) times) 0 0 0 0 0 0 2 34.22 36.22 32.22 34.72 34.45 4 59.11 61.11 57.11 58.11 58.91 6 81.53 82.53 79.3 80.53 81.07 10 94.78 95.78 93.78 93.978 94.18 15 100 100 100 100 100 20 100 100 100 100 100 Recovery 99.87 99.65 99.72 99.68 99.57 rate (%)

[0088] It can be seen from table 5 that: in a cyclic degradation experiment of degradation of the ciprofloxacin by catalytically activating the PMS with the ZSM-5-(C@Fe), it can be clearly found that with increase of cycle times, the removal rate of the ciprofloxacin is basically stable, and the catalyst may be almost completely recovered. Therefore, the ZSM-5-(C@Fe) may still catalytically activating the PMS effectively to degrade the ECs after many cycles.

[0089] The above embodiments are only the preferred embodiments of the present invention, which are only used to explain the present invention, and are not intended to limit the present invention. The changes, substitutions, modifications, and the like made by those skilled in the art without departing from the spirit of the present invention shall belong to the scope of protection of the present invention.