A kind of chloroquine phosphate remover and its preparation method and application

Abstract

The present application provides a kind of chloroquine phosphate remover and preparation method and application, belong to the technical field of chloroquine phosphate removal. The preparation method provided by the present application includes the following steps: polyphenols, formaldehyde and iron source are placed in water, catalyst is added to stir and dissolve, the obtained solution is transferred to a microwave reaction tube for reaction, the solution after reaction is cooled and filtered to obtain filter residue, and the filter residue is washed with ethanol to obtain iron-doped polyphenol-formaldehyde resin microspheres; ammonium molybdate, thiourea and iron source are placed in water and stirred, and the obtained solution is transferred to an autoclave for reaction, and the solution after reaction is cooled and filtered to obtain filter residue, i.e. iron-doped molybdenum disulfide nanoflowers; iron-doped polyphenol-formaldehyde resin microspheres and iron-doped molybdenum disulfide nanoflowers are ball-milled and mixed according to a certain ratio to obtain chloroquine phosphate remover. The present application can improve the removal rate of chloroquine phosphate, and does not produce by-products such as nitroaromatic compounds, avoiding secondary pollution of water bodies.

Description

Technical Field

[0001] The present application belongs to the technical field of chloroquine phosphate removal, and specifically relates to a chloroquine phosphate remover and a preparation method and application thereof. Background Art

[0002] Chloroquine phosphate can be used to treat and prevent malaria, amebiasis and rheumatoid arthritis. Chloroquine phosphate is highly water-soluble, toxic, difficult to degrade and persistent. It enters the soil and wastewater as medical waste, posing a potential threat to organisms and the environment, so it needs to be removed.

[0003] In the related art, the removal method of chloroquine phosphate mainly adopts the oxidation process based on peroxymonosulfate and the oxidation process based on H2O2, which uses peroxymonosulfate to activate under ultraviolet light to produce strong oxidizing sulfate free radicals (·SO4 - ) and hydroxyl radicals (·HO), which can effectively remove chloroquine phosphate, but will produce by-products such as nitroaromatic compounds, causing secondary pollution to the water body.

[0004] Therefore, it is necessary to provide a chloroquine phosphate remover and preparation method and application thereof to solve the problems raised in the above-mentioned background technology. Summary of the invention

[0005] The present application provides a chloroquine phosphate remover and a preparation method and application thereof. The large specific surface area and negative charge of molybdenum disulfide nanoflowers are used to electrostatically adsorb chloroquine phosphate; and under photocatalytic conditions, polyphenol-formaldehyde resin microspheres produce highly oxidizing H2O2 and hydroxyl radicals (·OH) to degrade chloroquine phosphate. The two methods are combined to improve the removal rate of chloroquine phosphate, and no byproducts such as nitroaromatic compounds are produced in the removal process, and no secondary pollution is caused to the water body. The present invention can be applied to the removal of chloroquine phosphate of different concentrations in medical and pharmaceutical wastewater.

[0006] In order to solve the above technical problems, the technical solution of this application is:

[0007] A preparation method of a chloroquine phosphate remover comprises the steps:

[0008] Step S1, placing polyphenol, formaldehyde and an iron source in water, adding a catalyst and stirring to dissolve, transferring the obtained solution to a microwave reaction tube for reaction, cooling and filtering the solution after the reaction to obtain a filter residue, and washing the filter residue with ethanol to obtain iron-doped polyphenol-formaldehyde resin microspheres;

[0009] Step S2, adding ammonium molybdate, thiourea and an iron source to water and stirring the solution, transferring the obtained solution to an autoclave for reaction, cooling and filtering the solution after the reaction in sequence to obtain a filter residue, namely, iron-doped molybdenum disulfide nanoflowers;

[0010] Step S3, ball-milling and mixing the iron-doped polyphenol-formaldehyde resin microspheres and the iron-doped molybdenum disulfide nanoflowers in a certain proportion to obtain a chloroquine phosphate remover.

[0011] Preferably, the polyphenol is selected from at least one of phenol, tea polyphenols and resorcinol.

[0012] Preferably, the mass ratio of the polyphenols to formaldehyde is 1:2.

[0013] Preferably, the catalyst is selected from any one of boric acid, acetic acid and oxalic acid.

[0014] Preferably, the iron source is selected from one of ferric chloride, ferrous sulfate, ferrous oxalate, ferric citrate and iron carbon dots.

[0015] Preferably, the reaction temperature in step S1 is 180-250° C., and the reaction time is 10-30 min.

[0016] Preferably, in step S3, the addition ratio of iron-doped-polyphenol-formaldehyde resin microspheres and iron-doped-molybdenum disulfide nanoflowers is 1:10-10:1.

[0017] Preferably, in step S3, the ball milling speed is 500-5000 rpm, and the ball milling time is 5-50 s.

[0018] A chloroquine phosphate remover is prepared by adopting the preparation method of the chloroquine phosphate remover.

[0019] An application of the above-mentioned chloroquine phosphate remover is used to remove chloroquine phosphate under visible light conditions, and the maximum adsorption capacity for chloroquine phosphate is 165.9 mg / g.

[0020] The beneficial effects of this application are:

[0021] Molybdenum disulfide is negatively charged and chloroquine phosphate is positively charged. Based on electrostatic interaction, chloroquine phosphate can be well enriched on the surface of molybdenum disulfide, so that molybdenum disulfide has a good adsorption effect on chloroquine phosphate; the nanoflower morphology constructed by iron-doped-molybdenum disulfide nanoflowers during the synthesis process increases the active surface area, which can further enhance the adsorption effect; under visible light conditions, iron-doped-polyphenol-formaldehyde resin microspheres can continuously produce a high concentration of H2O2, which is in situ catalytically decomposed into a variety of oxide active substances by MoS2 with peroxidase-like activity, and oxidizes chloroquine phosphate into carbon dioxide and water; the combination of the two methods can improve the removal rate of chloroquine phosphate, and no by-products such as nitroaromatic compounds are produced in the removal process, and no secondary pollution is caused to the water body. It can be used for the removal of chloroquine phosphate of different concentrations in medical and pharmaceutical wastewater. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 It is a graph showing the adsorption capacity of samples for chloroquine phosphate under different embodiments;

[0023] Figure 2 It is the removal rate diagram of chloroquine phosphate by the samples under different embodiments;

[0024] Figure 3 The surface morphology of Fe-CRF in Example 1 is shown in a scanning electron microscope image;

[0025] Figure 4 This is a scanning electron microscope image of the surface morphology of Fe-MoS2 in Example 2. DETAILED DESCRIPTION

[0026] The following will be combined with the drawings in the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0027] Please refer to Figure 1 and Figure 4 The present application provides a method for preparing a chloroquine phosphate remover, comprising the following steps:

[0028] Step S1, placing polyphenol, formaldehyde and an iron source in water, adding a catalyst and stirring to dissolve, transferring the obtained solution to a microwave reaction tube for reaction, cooling and filtering the solution after the reaction to obtain a filter residue, and washing the filter residue with ethanol to obtain iron-doped polyphenol-formaldehyde resin microspheres;

[0029] Step S2, adding ammonium molybdate, thiourea and an iron source to water and stirring the solution, transferring the obtained solution to an autoclave for reaction, cooling and filtering the solution after the reaction in sequence to obtain a filter residue, namely, iron-doped molybdenum disulfide nanoflowers;

[0030] Step S3, ball-milling and mixing the iron-doped polyphenol-formaldehyde resin microspheres and the iron-doped molybdenum disulfide nanoflowers in a certain proportion to obtain a chloroquine phosphate remover.

[0031] Preferably, the polyphenol is selected from at least one of phenol, tea polyphenols and resorcinol.

[0032] Preferably, the mass ratio of the polyphenols to formaldehyde is 1:2.

[0033] Preferably, the catalyst is selected from any one of boric acid, acetic acid and oxalic acid.

[0034] Preferably, the iron source is selected from one of ferric chloride, ferrous sulfate, ferrous oxalate, ferric citrate and iron carbon dots.

[0035] Preferably, the reaction temperature in step S1 is 180-250° C., and the reaction time is 10-30 min.

[0036] Preferably, in step S3, the addition ratio of iron-doped-polyphenol-formaldehyde resin microspheres and iron-doped-molybdenum disulfide nanoflowers is 1:10-10:1.

[0037] Preferably, in step S3, the ball milling speed is 500-5000 rpm, and the ball milling time is 5-50 s.

[0038] The present application also provides a chloroquine phosphate remover, which is prepared using the above-mentioned preparation method of the chloroquine phosphate remover.

[0039] The present application also provides an application of the above-mentioned chloroquine phosphate remover, which is used to remove chloroquine phosphate under visible light conditions, and the maximum adsorption capacity for chloroquine phosphate is 165.9 mg / g.

[0040] The chloroquine phosphate remover prepared in the present application is a composite material of iron-doped-polyphenol-formaldehyde resin microspheres and iron-doped-molybdenum disulfide nanoflowers (Fe-CRF@MoS2), with iron-doped-polyphenol-formaldehyde resin microspheres as the core, and iron-doped-molybdenum disulfide nanoflowers coated on the surface of the iron-doped-polyphenol-formaldehyde resin microspheres.

[0041] The removal principle of chloroquine phosphate by the chloroquine phosphate remover provided in the present application is:

[0042] (1) MoS2 is negatively charged and chloroquine phosphate is positively charged. Based on electrostatic interaction, chloroquine phosphate can be well enriched on the surface of MoS2, so that MoS2 has a good adsorption effect on chloroquine phosphate. The nanoflower morphology formed by iron-doped MoS2 nanoflowers during the synthesis process increases the active surface area, which can further improve the adsorption effect.

[0043] (2) Iron-doped polyphenol-formaldehyde resin microspheres are a semiconductor material with a strong π-stacking structure and a band gap of 1.8 eV. Under visible light conditions, the photogenerated electrons generated will promote the reduction of oxygen in water, continuously produce high concentrations of H2O2, and undergo a Fenton reaction with the doped Fe to oxidize chloroquine phosphate to an inorganic state. Molybdenum disulfide can promote the decomposition of the in-situ produced H2O2 into hydroxyl free radicals, and has a catalase-like function, which can improve the utilization efficiency of H2O2.

[0044] The chloroquine phosphate remover provided in the present application generates H2O2 in situ through a cascade reaction, eliminating the need for storage of H2O2. Molybdenum disulfide activates H2O2 to produce active substances (hydroxyl radicals, superoxide radicals, singlet oxygen, etc.), and can also remove bacteria, viruses, etc. in water.

[0045] Example 1

[0046] This embodiment provides a method for preparing iron-doped polyphenol-formaldehyde resin microspheres, comprising the following steps:

[0047] 10 mg of iron carbon dots, 0.7518 g of resorcinol, 0.016 g of tea polyphenols and 1.08 mL of formaldehyde were placed in a beaker, and 0.036 mL of oxalic acid and 50 mL of water were added. After magnetic stirring for 1 hour, the mixture was transferred to a 100 mL microwave reaction tube and reacted at 180 ° C for 10 minutes. After cooling, the mixture was taken out and filtered with a 0.22 μm organic filter membrane to obtain a red-black solid. The solid was washed with water and ethanol for 3 times and vacuum dried at 60 ° C for 24 hours to obtain iron-doped-polyphenol-formaldehyde resin microspheres (Fe-CRF).

[0048] Example 2

[0049] This embodiment provides a method for preparing iron carbon dots-molybdenum disulfide nanoflowers, comprising the following steps:

[0050] Add 1.96g of ammonium molybdate, 1.06g of thiourea, and 50mg of ferric chloride into 40mL of deionized water, stir until dissolved, transfer into a 100mL autoclave and keep at 180℃ for 24h, filter after cooling, wash the black powder with water and anhydrous ethanol, and dry at 60℃ in vacuum for 24h to obtain iron carbon dots-molybdenum disulfide nanoflowers (Fe-MoS2).

[0051] Example 3

[0052] The present embodiment provides a method for preparing a chloroquine phosphate remover, comprising the following steps:

[0053] Weigh 17.25 mg Fe-CRF and 2.5 mg Fe-MoS2 into a 2 mL PE tube and ball mill at 5000 rpm for 20 s to obtain the chloroquine phosphate remover.

[0054] Example 4

[0055] The present embodiment provides a method for preparing a chloroquine phosphate remover, comprising the following steps:

[0056] Weigh 15 mg Fe-CRF and 5 mg Fe-MoS2 into a 2 mL PE tube and ball mill at 5000 rpm for 20 s to obtain the chloroquine phosphate remover.

[0057] Example 5

[0058] The present embodiment provides a method for preparing a chloroquine phosphate remover, comprising the following steps:

[0059] Weigh 10 mg Fe-CRF and 10 mg Fe-MoS2 into a 2 mL PE tube and ball mill at 5000 rpm for 20 s to obtain the chloroquine phosphate remover.

[0060] Example 6

[0061] The present embodiment provides a method for preparing a chloroquine phosphate remover, comprising the following steps:

[0062] Weigh 5 mg Fe-CRF and 15 mg Fe-MoS2 into a 2 mL PE tube and ball mill at 5000 rpm for 20 s to obtain the chloroquine phosphate remover.

[0063] Example 7

[0064] The present embodiment provides a method for preparing a chloroquine phosphate remover, comprising the following steps:

[0065] Weigh 2.5 mg Fe-CRF and 17.5 mg Fe-MoS2 into a 2 mL PE tube and ball mill at 5000 rpm for 20 s to obtain the chloroquine phosphate remover.

[0066] Weigh 20 mg of each sample obtained in Example 1-7, place it in 50 mL of 20 mg / L chloroquine phosphate solution, stir for 30 min in the dark, and after reaching adsorption equilibrium, irradiate with a 300W xenon lamp (with a 420nm filter) at a distance of 8 cm from the light source. Take 2 mL of the suspension from the above solution every half an hour, filter it through a 0.22 μm filter membrane, and test the concentration of chloroquine phosphate over the illumination time. The test results are as follows: Figure 1 As shown. Figure 1 It can be seen that the maximum adsorption capacity of the chloroquine phosphate adsorbent provided in the present application for chloroquine phosphate is 165.9 mg / g.

[0067] The removal results of chloroquine phosphate by the samples obtained in Examples 1-7 are shown in Table 1:

[0068] Table 1 Results of removal of chloroquine phosphate by samples obtained from Examples 1-7

[0069]

[0070]

[0071] As can be seen from Table 1, iron-doped molybdenum disulfide nanoflowers have a strong adsorption capacity for chloroquine phosphate. By compounding with iron-doped polyphenol-formaldehyde resin microspheres, the photocatalytic degradation and removal effect of chloroquine phosphate under visible light is further enhanced, and chloroquine phosphate can be completely mineralized into inorganic substances such as carbon dioxide and water.

[0072] The embodiments of the present application are described above in conjunction with the accompanying drawings, but the present application is not limited to the above-mentioned specific implementation methods. The above-mentioned specific implementation methods are merely illustrative and not restrictive. Under the guidance of the present application, ordinary technicians in this field can also make many forms without departing from the purpose of the present application and the scope of protection of the claims, all of which are within the protection of the present application.

Claims

1. A preparation method for a chloroquine phosphate remover, characterized in that, The steps include: Step S1, placing polyphenol, formaldehyde and an iron source in water, adding a catalyst and stirring to dissolve, transferring the obtained solution to a microwave reaction tube for reaction, cooling and filtering the solution after the reaction to obtain a filter residue, and washing the filter residue with ethanol to obtain iron-doped polyphenol-formaldehyde resin microspheres; Step S2, placing ammonium molybdate, thiourea and an iron source in water to stir the solution, transferring the obtained solution to an autoclave for reaction, cooling and filtering the solution after the reaction to obtain a filter residue, namely, iron-doped molybdenum disulfide nanoflowers; Step S3, ball-milling and mixing the iron-doped polyphenol-formaldehyde resin microspheres and the iron-doped molybdenum disulfide nanoflowers in a certain proportion to obtain a chloroquine phosphate remover.

2. the preparation method of chloroquine phosphate remover according to claim 1, is characterized in that, The polyphenol is selected from at least one of tea polyphenols and resorcinol.

3. the preparation method of chloroquine phosphate remover according to claim 1, is characterized in that, The mass ratio of the polyphenols to formaldehyde is 1:

2.

4. the preparation method of chloroquine phosphate remover according to claim 1, is characterized in that, The catalyst is selected from any one of boric acid, acetic acid and oxalic acid.

5. the preparation method of chloroquine phosphate remover according to claim 1, is characterized in that, The iron source is selected from one of ferric chloride, ferrous sulfate, ferrous oxalate, ferric citrate and iron carbon dots.

6. the preparation method of chloroquine phosphate remover according to claim 1, is characterized in that, The reaction temperature in step S1 is 180-250° C., and the reaction time is 10-30 min.

7. the preparation method of chloroquine phosphate remover according to claim 1, is characterized in that, In step S3, the addition ratio of iron-doped polyphenol-formaldehyde resin microspheres and iron-doped molybdenum disulfide nanoflowers is 1:10-10:

1.

8. the preparation method of chloroquine phosphate remover according to claim 1, is characterized in that, In step S3, the ball milling speed is 500-5000 rpm, and the ball milling time is 5-50 s.

9. A chloroquine phosphate remover, characterized in that, The chloroquine phosphate remover is prepared by the preparation method of the chloroquine phosphate remover according to any one of claims 1 to 8.

10. An application of the chloroquine phosphate remover as claimed in claim 9, characterized in that, It is used to catalytically remove chloroquine phosphate under visible light conditions, and the maximum adsorption capacity for chloroquine phosphate is 165.9 mg / g.

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