CN114835218A

CN114835218A - Method for enhancing removal of As (III) and/or As (V) based on coupling of ferrous iron or ferric ion with peroxymonosulfate

Info

Publication number: CN114835218A
Application number: CN202210486063.7A
Authority: CN
Inventors: 李海普; 方颖; 蔡慧; 刘倩文; 张芸嘉
Original assignee: Central South University
Current assignee: Central South University
Priority date: 2022-05-06
Filing date: 2022-05-06
Publication date: 2022-08-02

Abstract

The invention discloses a method for enhancing removal of As (III) and/or As (V) based on coupling of ferrous iron or ferric ions with peroxymonosulfate, which is characterized in that a ferrous iron or ferric salt solution and a potassium hydrogen persulfate solution are added into a water body containing As (III) and/or As (V), and stirring is carried out at room temperature to complete the removal reaction of As (III) and/or As (V). The method of the invention can effectively and rapidly remove As (III) and/or As (V) by ferrous iron or ferric ion coupled peroxymonosulfate, and compared with a peroxydisulfate system with the quantitative concentration of ferrous iron or ferric ion coupled substances and a hydrogen peroxide system with the quantitative concentration of ferrous iron or ferric ion coupled substances, the removal of As (III) and/or As (V) can be obviously enhanced by ferrous iron or ferric ion coupled peroxymonosulfate.

Description

Method for enhancing removal of As (III) and/or As (V) based on coupling of ferrous iron or ferric ion with peroxymonosulfate

Technical Field

The invention relates to a method for enhancing removal of As (III) and/or As (V), in particular to a method for enhancing removal of As (III) and/or As (V) based on coupling of ferrous iron or ferric ion with peroxymonosulfate, and belongs to the technical field of water treatment.

Background

Inorganic arsenic (As) is one of the most common heavy metal pollutants, mainly resulting from man-made activities such As smelting, mining, applying pesticides and fertilizers, and burning fossil fuels. As has been shown, overexposure of As can lead to neurological diseases, organ damage, anemia and the like. Currently, arsenic has been listed as one of the important moderating pollutants. Therefore, the search for a technology and a method for rapidly removing inorganic arsenic in the polluted water body is an urgent problem which meets the national needs and needs to be solved urgently.

At present, common methods for removing As (III, V) in water bodies comprise electric flocculation, coagulation/precipitation, ion exchange, adsorption and the like. The coagulating agent has the advantages of low price, small harm to the environment, simple operation process and the like, so the coagulating technology is commonly used for removing As (III) or As (V) in the water body. However, for the efficient removal of inorganic arsenic in water, a high dosage of coagulant is often required to be added, so that a method for enhancing the coagulation effect is urgently sought, so that the utilization efficiency of the coagulant is greatly improved, and the industrial cost is reduced.

Disclosure of Invention

The invention aims to: in order to solve the inorganic arsenic pollution condition of the water body, the invention provides a method which not only can combine ferrous iron or ferric ion and peroxymonosulfate ion to convert As (III) into As (V), but also can remove both from the water body.

The technical scheme is as follows: the invention relates to a method for enhancing removal of As (III) and/or As (V) based on coupling of ferrous iron or ferric ion with peroxymonosulfate, which comprises the steps of adding ferrous salt solution or ferric salt solution and peroxymonosulfate solution into a water body containing As (III) and/or As (V), stirring at normal temperature for reaction, and filtering to complete removal of As (III) and/or As (V).

Wherein the reaction time is 10-60s under normal temperature stirring.

Wherein the concentration of As (III) and/or As (V) in the water body is 0.2-5.0 mg/L.

Wherein the pH of the body of water is greater than 3.7.

Wherein the concentration of the ferrous salt solution or the ferric salt solution in the water body is 62.5-500 mu M.

Wherein the concentration of the added peroxymonosulfate solution in the water body is 16-320 mu M.

The removal mechanism is: when the pH value of the water body is more than 3.7, ferric iron can form hydroxide oxide or hydroxide precipitate, and the precipitate can be used as an adsorbent to adsorb inorganic arsenic in the water body. However, the adsorption capacity of As (III) is very limited, and the adsorption capacity of the precipitate is very considerable for As (V), so that a divalent iron or trivalent iron and peroxymonosulfate coupling system can be used for quickly oxidizing As (III) into As (V), and simultaneously, ferrous ions in the divalent iron and peroxymonosulfate coupling system can be quickly oxidized into ferric ions. Ferric ions generated in the system or directly added can generate an adsorbent in situ to adsorb As (V), so as to efficiently and quickly remove As (III) and/or As (V), the method can effectively improve the removal effect of As (III) and As (V), and the operation process is simple and the treatment time is short.

Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: the ferrous ions or the ferric ions coupled with the peroxymonosulfate can effectively remove As (III) and As (V). Moreover, ferrous or ferric ion coupled peroxymonosulfates can significantly enhance the removal of as (iii) and as (v) compared to oxidant systems having ferrous or ferric ion coupled to other species concentrations. The method is simple to operate, strong in feasibility, excellent in effect and wide in industrial application prospect.

Drawings

FIG. 1 is a graph showing the effect of example 1, comparative example 1 and comparative example 7 on the removal of As (III);

FIG. 2 is a graph showing the oxidation effects of example 2, comparative example 2 and comparative example 8 on As (III);

FIG. 3 is a graph showing the effect of example 3, comparative example 9 and comparative example 13 on the removal of As (III);

FIG. 4 is a graph showing the oxidation effects of example 4, comparative example 10, and comparative example 14 on As (III);

FIG. 5 is a graph showing the effect of example 5, comparative example 5 and comparative example 11 on the removal of As (V);

FIG. 6 is a graph showing the effect of example 6, comparative example 12 and comparative example 15 on the removal of As (V);

FIG. 7 is a graph showing the effect of example 7 on the removal of As (III);

FIG. 8 is a graph showing the effect of example 8 on the removal of As (III);

FIG. 9 is a graph showing the effect of example 9 on the removal of As (III);

FIG. 10 is a graph showing the effect of example 10 on the removal of As (V);

FIG. 11 is a graph showing the effect of example 11 on the removal of As (V);

FIG. 12 is a graph showing the effect of example 12 on the removal of As (V);

FIG. 13 is a graph showing the effect of example 13 on the removal of As (III);

FIG. 14 is a graph showing the effect of example 14 on the removal of As (III);

FIG. 15 is a graph showing the effect of example 15 on the removal of As (III);

FIG. 16 is a graph showing the effect of example 16 on the removal of As (V);

FIG. 17 is a graph showing the effect of example 17 on the removal of As (V);

FIG. 18 is a graph showing the effect of example 18 on the removal of As (V);

FIG. 19 is a graph of the mean particle size of flocs produced by different systems.

Detailed Description

The technical scheme of the invention is further explained by combining the attached drawings.

Preparation of As (III) and As (V) solutions: as (III) solution is prepared by mixing sodium arsenite (NaAsO) ₂ ) Dissolving in ultrapure water to obtain a solution with a concentration of 0.2-5.0mg/L, and adjusting the pH of the aqueous solution to be more than 3.7; as (V) solution is sodium arsenate dodecahydrate (NaHAsO) ₄ ·12H ₂ O) is dissolved in ultrapure water, the concentration of the solution is 0.2-5.0mg/L, and the pH value of the aqueous solution is adjusted to be more than 3.7.

Preparation of a peroxymonosulfate stock solution: the concentration of the prepared potassium hydrogen persulfate is 49.9-50.1 g/L.

Preparing a ferrite stock solution: the concentration of the prepared ferrous ions is 0.249-0.251 mol/L.

Preparing a ferric salt stock solution: the concentration of the prepared iron ions is 0.249-0.251 mol/L.

Example 1 efficient and Rapid removal of As (III) based on ferrous ion coupling of Peronosulfate

First, 50mL of As (III) solution was taken in a 100 mL-volume Erlenmeyer flask, and the solution was left to stir at room temperature. Respectively transferring 50 mu L of ferrite stock solution and 75 mu L of peroxymonosulfate stock solution by using a precision pipettor, simultaneously adding the ferrite stock solution and the peroxymonosulfate stock solution into the conical flask, starting timing, taking 1mL of water in the conical flask by using the pipettor every 10s within 10-60s, quickly passing through a 0.22 mu m water-system filter membrane, detecting the signal response value of the residual total arsenic in the filtered water by using an inductive coupling plasma mass spectrometer, establishing a standard curve of the total arsenic in the water strictly according to an HJ-7002014 standard file, wherein the standard curve range of the total arsenic is 1-200 mu g/L, R is 1-200 mu g/L ² 0.9999. The concentration of the residual total arsenic in the water body is found on a standard curve of the total arsenic in the water body according to the measured signal response value of the residual total arsenic in the water body, and the result is shown in fig. 1. As can be seen from FIG. 1, the removal effect of the ferrous ion-coupled peroxymonosulfate system on As (III) is significantly better than that of the ferrous ion-coupled peroxydisulfate system and the ferrous ion-coupled hydrogen peroxide system.

Example 2 efficient fast As (III) Oxidation based on ferrous ion coupling Peronosulfate

First, 50mL of As (III) solution was taken in a 100 mL-volume Erlenmeyer flask, and the solution was left to stir at room temperature. Respectively transferring 50 mu L of ferrite stock solution and 75 mu L of peroxymonosulfate stock solution by using a precision pipettor, simultaneously adding the ferrite stock solution and the peroxymonosulfate stock solution into the conical flask, starting timing, taking 4mL of water in the conical flask by using the pipettor every 10s within 10s-60s, quickly adding the water into 2% hydrochloric acid and a color developing agent which are prepared in advance, and then detecting the absorbance of As (V) in the water by using an ultraviolet-visible spectrophotometer. Wherein, the volume of the 2% hydrochloric acid is 0.3mL, the volume of the color developing agent is 0.3mL, and the color developing agent comprises 10.8% ascorbic acid, 3% ammonium molybdate tetrahydrate, 0.56% antimony potassium tartrate and 13.98% sulfuric acid. A standard curve of As (V) content was established according to the literature (environ. Sci. Technol.2014,48,3978- ² 0.9997. Checking the standard curve of As (V) content according to the measured As (V) absorbance in the water bodyAs (V) concentration was obtained, and the results are shown in FIG. 2.

Example 3 high efficiency fast As (III) removal based on iron ion coupling peroxymonosulfate

First, 50mL of As (III) solution was taken in a 100 mL-volume Erlenmeyer flask, and the solution was left to stir at room temperature. Respectively transferring 50 mu L of iron salt stock solution and 75 mu L of peroxymonosulfate stock solution by using a precision pipettor, simultaneously adding the two into the conical flask, starting timing, transferring 1mL of water in the conical flask by using the pipettor every 10s within 10s-60s, rapidly passing through a 0.22 mu m water system filter membrane, and then detecting the response value of residual total arsenic signals in the filtered water by using an inductively coupled plasma mass spectrometer. According to the measured signal response value of the total arsenic remaining in the water body, the concentration of the total arsenic remaining in the water body is found on the standard curve of the total arsenic in the water body in example 1, and the result is shown in fig. 3.

Example 4 efficient fast As (III) Oxidation based on iron ion coupled Peronosulfate

First, 50mL of As (III) solution was taken in a 100 mL-volume Erlenmeyer flask, and the solution was left to stir at room temperature. Respectively transferring 50 mu L of iron salt stock solution and 75 mu L of peroxymonosulfate stock solution by using a precision pipette, simultaneously adding the two into the conical flask, starting timing, taking 4mL of water in the conical flask by using the pipette every 10s within 10s-60s, quickly adding the water into 2% hydrochloric acid prepared in advance and the color developing agent in the embodiment 2, and then detecting the absorbance of As (V) in the water by using an ultraviolet-visible spectrophotometer. According to the measured absorbance of As (V) in the water body, the concentration of As (V) is found on the standard curve of the content of As (V) in example 2, and the result is shown in FIG. 4.

Example 5 efficient and Rapid removal of As (V) based on coupling of ferrous ions to Monosulfate

First, 50mL of As (V) solution was taken in a 100 mL-volume Erlenmeyer flask, and the solution was left to stir at room temperature. Respectively transferring 50 mu L of ferrite stock solution and 75 mu L of peroxymonosulfate stock solution by using a precision pipettor, simultaneously adding the ferrite stock solution and the peroxymonosulfate stock solution into the conical flask, starting timing, transferring 1mL of water in the conical flask by using the pipettor every 10s within 10s-60s, rapidly passing through a 0.22 mu m water system filter membrane, and then detecting the response value of the residual total arsenic signals in the filtered water by using an inductively coupled plasma mass spectrometer. According to the measured signal response value of the total arsenic remaining in the water body, the concentration of the total arsenic remaining in the water body was found on the standard curve of the total arsenic in the water body in example 1, and the result is shown in fig. 5.

Example 6 efficient and Rapid removal of As (V) based on iron ion coupling Peronosulfate

First, 50mL of As (V) solution was taken in a 100 mL-volume Erlenmeyer flask, and the solution was left to stir at room temperature. Respectively transferring 50 mu L of iron salt stock solution and 75 mu L of peroxymonosulfate stock solution by a precision pipettor, simultaneously adding the two into the conical flask, starting timing, transferring 1mL of water in the conical flask by the pipettor every 10s within 10s-60s, rapidly passing through a 0.22 mu m water system filter membrane, and detecting the residual total arsenic signal response value by an inductively coupled plasma mass spectrometer. According to the measured signal response value of the total arsenic remaining in the water body, the concentration of the total arsenic remaining in the water body is found on the standard curve of the total arsenic in the water body in example 1, and the result is shown in fig. 6.

Example 7 removal of As (III) based on different ferrous ion concentrations in ferrous ion coupled monopersulfate

First, 50mL of As (III) solution was taken in a 100 mL-volume Erlenmeyer flask, and the solution was left to stir at room temperature. Respectively transferring 12.5, 25, 37.5, 50, 75, 100 mu L of ferrite stock solution and 75 mu L of peroxymonosulfate stock solution by using a precision pipettor, simultaneously adding the two into the conical flask, starting timing, within 10s-60s, taking 1mL of water in the conical flask by using the pipettor every 10s, rapidly passing through a 0.22 mu m water system filter membrane, and then detecting the residual total arsenic signal response value in the sample by using an inductively coupled plasma mass spectrometer. According to the measured signal response value of the total arsenic remaining in the water body, the concentration of the total arsenic remaining in the water body is found on the standard curve of the total arsenic in the water body in example 1, and the result is shown in fig. 7.

Example 8 removal of As (III) based on different Peronosulfate concentrations in ferrous ion coupled Peronosulfate removal of As (III)

First, 50mL of As (III) solution was taken in a 100 mL-volume Erlenmeyer flask, and the solution was left to stir at room temperature. Respectively transferring 50 mu L of ferrite stock solution and 5, 10, 25, 50, 75 and 100 mu L of peroxymonosulfate stock solution by using a precision pipettor, simultaneously adding the ferrite stock solution and the peroxymonosulfate stock solution into the conical flask, starting timing, transferring 1mL of water in the conical flask by using the pipettor every 10s within 10s-60s, rapidly passing through a 0.22 mu m water system filter membrane, and then detecting the response value of the residual total arsenic signal in the sample by using an inductively coupled plasma mass spectrometer. According to the measured signal response value of the total arsenic remaining in the water body, the concentration of the total arsenic remaining in the water body was found on the standard curve of the total arsenic in the water body in example 1, and the result is shown in fig. 8.

Example 9 removal of As (III) at various concentrations based on ferrous ion coupling to Permonosulfate

First, 50mL of As (III) solutions having concentrations of 0.2, 0.5, 1, 1.5, 2, and 5mg/L were measured in a 100mL Erlenmeyer flask, and the solution was stirred at room temperature. Respectively transferring 50 mu L ferrite stock solution and 75 mu L peroxymonosulfate stock solution by using a precision pipettor, simultaneously adding the ferrite stock solution and the peroxymonosulfate stock solution into the conical flask, starting timing, transferring 1mL water in the conical flask by using the pipettor every 10s within 10s-60s, rapidly passing through a 0.22 mu m water system filter membrane, and then detecting the response value of the residual total arsenic signal in the sample by using an inductively coupled plasma mass spectrometer. According to the measured signal response value of the total arsenic remaining in the water body, the concentration of the total arsenic remaining in the water body was found on the standard curve of the total arsenic in the water body in example 1, and the result is shown in fig. 9.

Example 10 removal of As (V) based on different ferrous ion concentrations in ferrous ion coupled peroxymonosulfate removal

First, 50mL of As (V) solution was taken in a 100 mL-volume Erlenmeyer flask, and the solution was left to stir at room temperature. Respectively transferring 12.5, 25, 37.5, 50, 75, 100 mu L of ferrite stock solution and 75 mu L of peroxymonosulfate stock solution by using a precision pipettor, simultaneously adding the two into the conical flask, starting timing, within 10s-60s, taking 1mL of water in the conical flask by using the pipettor every 10s, rapidly passing through a 0.22 mu m water system filter membrane, and then detecting the residual total arsenic signal response value in the sample by using an inductively coupled plasma mass spectrometer. According to the measured signal response value of the total arsenic remaining in the water body, the concentration of the total arsenic remaining in the water body was found on the standard curve of the total arsenic in the water body in example 1, and the result is shown in fig. 10.

Example 11 removal of As (V) based on different Peronosulfate concentrations in ferrous ion coupled Peronosulfate removal

First, 50mL of As (V) solution was taken in a 100 mL-volume Erlenmeyer flask, and the solution was left to stir at room temperature. Respectively transferring 50 mu L of ferrite stock solution and 5, 10, 25, 50, 75 and 100 mu L of peroxymonosulfate stock solution by using a precision pipettor, simultaneously adding the ferrite stock solution and the peroxymonosulfate stock solution into the conical flask, starting timing, transferring 1mL of water in the conical flask by using the pipettor every 10s within 10s-60s, rapidly passing through a 0.22 mu m water system filter membrane, and then detecting the response value of the residual total arsenic signal in the sample by using an inductively coupled plasma mass spectrometer. According to the measured signal response value of the total arsenic remaining in the water body, the concentration of the total arsenic remaining in the water body was found on the standard curve of the total arsenic in the water body in example 1, and the result is shown in fig. 11.

Example 12 removal of As (V) at various concentrations based on ferrous ion coupling to Permonosulfate

First, 50mL of As (V) solutions having concentrations of 0.2, 0.5, 1, 1.5, 2, and 5mg/L were measured in a 100mL Erlenmeyer flask, and the solution was stirred at room temperature. Respectively transferring 50 mu L of ferrite stock solution and 75 mu L of peroxymonosulfate stock solution by using a precision pipettor, simultaneously adding the ferrite stock solution and the peroxymonosulfate stock solution into the conical flask, starting timing, taking 1mL of water in the conical flask by using the pipettor every 10s within 10s-60s, quickly passing through a 0.22 mu m water system filter membrane, and then detecting a residual total arsenic signal response value in a sample by using an inductively coupled plasma mass spectrometer. According to the measured signal response value of the total arsenic remaining in the water body, the concentration of the total arsenic remaining in the water body was found on the standard curve of the total arsenic in the water body in example 1, and the result is shown in fig. 12.

Example 13 As (III) removal based on iron ion coupling Peronosulfate removal at different iron ion concentrations

First, 50mL of As (III) solution was taken in a 100 mL-volume Erlenmeyer flask, and the solution was left to stir at room temperature. Respectively transferring 12.5, 25, 37.5, 50, 75 and 100 mu L of ferric salt stock solution and 75 mu L of peroxymonosulfate stock solution by using a precision pipettor, simultaneously adding the ferric salt stock solution and the 75 mu L of peroxymonosulfate stock solution into the conical flask, starting timing, within 10s-60s, taking 1mL of water in the conical flask by using the pipettor every 10s, rapidly passing through a 0.22 mu m water system filter membrane, and then detecting the residual total arsenic signal response value in the sample by using an inductively coupled plasma mass spectrometer. According to the measured signal response value of the total arsenic remaining in the water body, the concentration of the total arsenic remaining in the water body was found on the standard curve of the total arsenic in the water body in example 1, and the result is shown in fig. 13.

Example 14 As (III) removal based on different Peronosulfate concentrations in iron ion coupled Peronosulfate removal

First, 50mL of As (III) solution was taken in a 100 mL-volume Erlenmeyer flask, and the solution was left to stir at room temperature. Respectively transferring 50 mu L of ferric salt stock solution and 5, 10, 25, 50, 75 and 100 mu L of peroxymonosulfate stock solution by using a precision pipettor, simultaneously adding the two into the conical flask, starting timing, transferring 1mL of water in the conical flask by using the pipettor every 10s within 10s-60s, rapidly passing through a 0.22 mu m water system filter membrane, and then detecting the response value of the residual total arsenic signal in the sample by using an inductively coupled plasma mass spectrometer. According to the measured signal response value of the total arsenic remaining in the water body, the concentration of the total arsenic remaining in the water body was found on the standard curve of the total arsenic in the water body in example 1, and the result is shown in fig. 14.

Example 15 removal of As (III) at various concentrations based on iron ion coupling of Permonosulfate

First, 50mL of As (III) solutions having concentrations of 0.2, 0.5, 1, 1.5, 2, and 5mg/L were measured in a 100mL Erlenmeyer flask, and the solution was stirred at room temperature. Respectively transferring 50 mu L of ferric salt stock solution and 75 mu L of peroxymonosulfate stock solution by using a precision pipettor, simultaneously adding the ferric salt stock solution and the peroxymonosulfate stock solution into the conical flask, starting timing, transferring 1mL of water in the conical flask by using the pipettor every 10s within 10s-60s, rapidly passing through a 0.22 mu m water system filter membrane, and then detecting the response value of the residual total arsenic signal in the sample by using an inductively coupled plasma mass spectrometer. According to the measured signal response value of the total arsenic remaining in the water body, the concentration of the total arsenic remaining in the water body was found on the standard curve of the total arsenic in the water body in example 1, and the result is shown in fig. 15.

Example 16 removal of As (V) based on different concentrations of iron ions in iron ion coupled permonosulfate removal of As (V)

First, 50mL of As (V) solution was taken in a 100 mL-volume Erlenmeyer flask, and the solution was left to stir at room temperature. Respectively transferring 12.5, 25, 37.5, 50, 75 and 100 mu L of ferric salt stock solution and 75 mu L of peroxymonosulfate stock solution by using a precision pipettor, simultaneously adding the ferric salt stock solution and the 75 mu L of peroxymonosulfate stock solution into the conical flask, starting timing, within 10s-60s, taking 1mL of water in the conical flask by using the pipettor every 10s, rapidly passing through a 0.22 mu m water system filter membrane, and then detecting the residual total arsenic signal response value in the sample by using an inductively coupled plasma mass spectrometer. According to the measured signal response value of the total arsenic remaining in the water body, the concentration of the total arsenic remaining in the water body was found on the standard curve of the total arsenic in the water body in example 1, and the result is shown in fig. 16.

Example 17 removal of As (V) based on different concentrations of Peronosulfate in iron ion coupled Peronosulfate removal of As (V)

First, 50mL of As (V) solution was taken in a 100 mL-volume Erlenmeyer flask, and the solution was left to stir at room temperature. Respectively transferring 50 mu L of ferric salt stock solution and 5, 10, 25, 50, 75 and 100 mu L of peroxymonosulfate stock solution by using a precision pipettor, simultaneously adding the two into the conical flask, starting timing, transferring 1mL of water in the conical flask by using the pipettor every 10s within 10s-60s, rapidly passing through a 0.22 mu m water system filter membrane, and then detecting the response value of the residual total arsenic signal in the sample by using an inductively coupled plasma mass spectrometer. According to the measured signal response value of the total arsenic remaining in the water body, the concentration of the total arsenic remaining in the water body was found on the standard curve of the total arsenic in the water body in example 1, and the result is shown in fig. 17.

Example 18 removal of As (V) at various concentrations based on iron ion coupling of Permonosulfate

First, 50mL of As (V) solutions having concentrations of 0.2, 0.5, 1, 1.5, 2, and 5mg/L were measured in a 100mL Erlenmeyer flask, and the solution was stirred at room temperature. Respectively transferring 50 mu L of ferric salt stock solution and 75 mu L of peroxymonosulfate stock solution by using a precision pipettor, simultaneously adding the ferric salt stock solution and the peroxymonosulfate stock solution into the conical flask, starting timing, transferring 1mL of water in the conical flask by using the pipettor every 10s within 10s-60s, rapidly passing through a 0.22 mu m water system filter membrane, and then detecting the response value of the residual total arsenic signal in the sample by using an inductively coupled plasma mass spectrometer. According to the measured signal response value of the total arsenic remaining in the water body, the concentration of the total arsenic remaining in the water body was found on the standard curve of the total arsenic in the water body in example 1, and the result is shown in fig. 18.

Comparative example 1 method for removing As (III) based on ferrous ion-coupled peroxodisulfate

First, 50mL of As (III) solution was taken out into a 100 mL-volume Erlenmeyer flask, and the solution was left to stir at room temperature. Respectively transferring 50 mu L of ferrite stock solution and 75 mu L of peroxydisulfate stock solution by a precision pipettor, simultaneously adding the ferrite stock solution and the peroxydisulfate stock solution into the conical flask, starting timing, transferring 1mL of water in the conical flask by the pipettor every 10s within 10s-60s, rapidly passing through a 0.22 mu m water system filter membrane, and then detecting the response value of the residual total arsenic signal in the sample by an inductively coupled plasma mass spectrometer. According to the measured signal response value of the total arsenic remaining in the water body, the concentration of the total arsenic remaining in the water body is found on the standard curve of the total arsenic in the water body in example 1, and the result is shown in fig. 1.

Comparative example 2 method for the oxidation of As (III) based on the coupling of ferrous ions to peroxodisulfate

First, 50mL of As (III) solution was taken in a 100 mL-volume Erlenmeyer flask, and the solution was left to stir at room temperature. Respectively transferring 50 mu L of ferrite stock solution and 75 mu L of peroxydisulfate stock solution by a precision pipettor, simultaneously adding the ferrite stock solution and the peroxydisulfate stock solution into the conical flask, timing, taking 4mL of water in the conical flask by the pipettor every 10s within 10s-60s, rapidly adding the water into 2% hydrochloric acid prepared in advance and the color developing agent in the example 2, and then detecting the absorbance of As (V) in the water by an ultraviolet-visible spectrophotometer. According to the measured absorbance of As (V) in the water body, the concentration of As (V) is checked on a standard curve of the content of As (V) in the example 2, and the result is shown in figure 2.

Comparative example 3 method for removing As (III) based on iron ion-coupled peroxodisulfate

First, 50mL of As (III) solution was taken in a 100 mL-volume Erlenmeyer flask, and the solution was left to stir at room temperature. Respectively transferring 50 mu L of iron salt stock solution and 75 mu L of peroxydisulfate stock solution by a precision pipettor, simultaneously adding the two into the conical flask, starting timing, transferring 1mL of water in the conical flask by the pipettor every 10s within 10s-60s, rapidly passing through a 0.22 mu m water system filter membrane, and detecting the response value of residual total arsenic signals in the filtered water by an inductively coupled plasma mass spectrometer. According to the measured signal response value of the total arsenic remaining in the water body, the concentration of the total arsenic remaining in the water body is found on the standard curve of the total arsenic in the water body in example 1, and the result is shown in fig. 3.

Comparative example 4 method for oxidizing As (III) based on iron ion coupled peroxodisulfate

First, 50mL of As (III) solution was taken in a 100 mL-volume Erlenmeyer flask, and the solution was left to stir at room temperature. And respectively removing 50 mu L of iron salt stock solution and 75 mu L of peroxydisulfate stock solution by using a precision pipettor, simultaneously adding the iron salt stock solution and the peroxydisulfate stock solution into the conical flask, timing, removing 4mL of water in the conical flask by using the pipettor every 10s within 10s-60s, quickly adding the water into 2% hydrochloric acid prepared in advance and the color developing agent in the example 2, and detecting the absorbance of As (V) in the sample by using an ultraviolet-visible spectrophotometer. According to the measured absorbance of As (V) in the water body, the concentration of As (V) is found on the standard curve of the content of As (V) in example 2, and the result is shown in FIG. 4.

Comparative example 5 method for As (V) removal based on ferrous ion coupling peroxodisulfate

First, 50mL of As (V) solution was taken in a 100 mL-volume Erlenmeyer flask, and the solution was left to stir at room temperature. Respectively transferring 50 mu L of ferrite stock solution and 75 mu L of peroxydisulfate stock solution by a precision pipettor, simultaneously adding the ferrite stock solution and the peroxydisulfate stock solution into the conical flask, starting timing, transferring 1mL of water in the conical flask by the pipettor every 10s within 10s-60s, rapidly passing through a 0.22 mu m water system filter membrane, and detecting the response value of residual total arsenic signals in the filtered water by an inductively coupled plasma mass spectrometer. According to the measured signal response value of the total arsenic remaining in the water body, the concentration of the total arsenic remaining in the water body was found on the standard curve of the total arsenic in the water body in example 1, and the result is shown in fig. 5.

Comparative example 6 method for removing As (V) based on iron ion-coupled peroxodisulfate

First, 50mL of As (V) solution was taken in a 100 mL-volume Erlenmeyer flask, and the solution was left to stir at room temperature. Respectively removing 50 mu L of iron salt stock solution and 75 mu L of peroxydisulfate stock solution by a precision pipettor, simultaneously adding the two into the conical flask, starting timing, removing 1mL of water in the conical flask by the pipettor every 10s within 10s-60s, quickly passing through a 0.22 mu m water system filter membrane, and detecting the response value of the residual total arsenic signal in the filtered water by an inductively coupled plasma mass spectrometer. According to the measured signal response value of the total arsenic remaining in the water body, the concentration of the total arsenic remaining in the water body was found on the standard curve of the total arsenic in the water body in example 1, and the result is shown in fig. 6.

Comparative example 7 method for removing As (III) based on ferrous ion coupling hydrogen peroxide

First, 50mL of As (III) solution was taken in a 100 mL-volume Erlenmeyer flask, and the solution was left to stir at room temperature. Respectively transferring 50 mu L of ferrite stock solution and 75 mu L of hydrogen peroxide stock solution by using a precision pipettor, simultaneously adding the ferrite stock solution and the hydrogen peroxide stock solution into the conical flask, starting timing, transferring 1mL of water in the conical flask by using the pipettor every 10s within 10s-60s, rapidly passing through a 0.22 mu m water system filter membrane, and then detecting a residual total arsenic signal response value in the filtered water by using an inductively coupled plasma mass spectrometer. According to the measured signal response value of the total arsenic remaining in the water body, the concentration of the total arsenic remaining in the water body is found on the standard curve of the total arsenic in the water body in example 1, and the result is shown in fig. 1.

Comparative example 8 method for oxidizing As (III) peroxide based on coupling of ferrous ions

First, 50mL of As (III) solution was taken out into a 100 mL-volume Erlenmeyer flask, and the solution was left to stir at room temperature. Respectively transferring 50 mu L of ferrite stock solution and 75 mu L of hydrogen peroxide stock solution by using a precision pipettor, simultaneously adding the ferrite stock solution and the hydrogen peroxide stock solution into the conical flask, starting timing, transferring 4mL of water in the conical flask by using the pipettor every 10s to 60s, quickly adding the water into the prepared 2% hydrochloric acid and the color developing agent in the embodiment 2, and then detecting the absorbance of As (V) in the water by using an ultraviolet-visible spectrophotometer. According to the measured absorbance of As (V) in the water body, the concentration of As (V) is found on the standard curve of the content of As (V) in example 2, and the result is shown in FIG. 2.

Comparative example 9 method for removing As (III) based on iron ion coupled hydrogen peroxide

First, 50mL of As (III) solution was taken in a 100 mL-volume Erlenmeyer flask, and the solution was left to stir at room temperature. Respectively transferring 50 mu L of iron salt stock solution and 75 mu L of hydrogen peroxide stock solution by using a precision pipettor, simultaneously adding the iron salt stock solution and the hydrogen peroxide stock solution into the conical flask, starting timing, transferring 1mL of water in the conical flask by using the pipettor every 10s within 10s-60s, rapidly passing through a 0.22 mu m water system filter membrane, and then detecting the response value of residual total arsenic signals in the filtered water by using an inductively coupled plasma mass spectrometer. According to the measured signal response value of the total arsenic remaining in the water body, the concentration of the total arsenic remaining in the water body is found on the standard curve of the total arsenic in the water body in example 1, and the result is shown in fig. 3.

Comparative example 10 Process for oxidizing As (III) with hydrogen peroxide based on coupling of iron ions

First, 50mL of As (III) solution was taken out into a 100 mL-volume Erlenmeyer flask, and the solution was left to stir at room temperature. Respectively transferring 50 mu L of iron salt stock solution and 75 mu L of hydrogen peroxide stock solution by using a precision pipettor, simultaneously adding the iron salt stock solution and the hydrogen peroxide stock solution into the conical flask, timing, transferring 4mL of water in the conical flask by using the pipettor every 10s within 10s-60s, quickly adding the water into 2% hydrochloric acid prepared in advance and the color developing agent in the example 2, and then detecting the absorbance of As (V) in the water by using an ultraviolet-visible spectrophotometer. According to the measured absorbance of As (V) in the water body, the concentration of As (V) is found on the standard curve of the content of As (V) in example 2, and the result is shown in FIG. 4.

Comparative example 11 method for removing As (V) based on ferrous ion coupling hydrogen peroxide

First, 50mL of As (V) solution was taken out into a 100 mL-volume Erlenmeyer flask, and the solution was left to stir at room temperature. Respectively transferring 50 mu L of ferrite stock solution and 75 mu L of hydrogen peroxide stock solution by using a precision pipettor, simultaneously adding the ferrite stock solution and the hydrogen peroxide stock solution into the conical flask, starting timing, transferring 1mL of sample by using the pipettor every 10s to quickly pass through a 0.22 mu m water system filter membrane within 10s-60s, and then detecting the response value of residual total arsenic signals in the filtered water body by using an inductively coupled plasma mass spectrometer. According to the measured signal response value of the total arsenic remaining in the water body, the concentration of the total arsenic remaining in the water body was found on the standard curve of the total arsenic in the water body in example 1, and the result is shown in fig. 5.

Comparative example 12 method for removing As (V) based on ferric ion coupled hydrogen peroxide

First, 50mL of As (V) solution was taken in a 100 mL-volume Erlenmeyer flask, and the solution was left to stir at room temperature. Respectively transferring 50 mu L of iron salt stock solution and 75 mu L of hydrogen peroxide stock solution by using a precision pipettor, simultaneously adding the two into the conical flask, starting timing, transferring 1mL of water in the conical flask by using the pipettor every 10s within 10s-60s, rapidly passing through a 0.22 mu m water system filter membrane, and detecting the response value of residual total arsenic signals in the filtered water by using an inductively coupled plasma mass spectrometer. According to the measured signal response value of the total arsenic remaining in the water body, the concentration of the total arsenic remaining in the water body is found on the standard curve of the total arsenic in the water body in example 1, and the result is shown in fig. 6.

Comparative example 13 method for removing As (III) based on iron ion system alone

First, 50mL of As (III) solution was taken in a 100 mL-volume Erlenmeyer flask, and the solution was left to stir at room temperature. And (3) transferring 50 mu L of iron salt stock solution into the conical flask by using a precision pipettor, starting timing, transferring 1mL of water in the conical flask by using the pipettor every 10s within 10s-60s, rapidly passing through a 0.22 mu m water system filter membrane, and detecting a response value of a residual total arsenic signal in the filtered water by using an inductively coupled plasma mass spectrometer. According to the measured signal response value of the total arsenic remaining in the water body, the concentration of the total arsenic remaining in the water body is found on the standard curve of the total arsenic in the water body in example 1, and the result is shown in fig. 3.

Comparative example 14 method for oxidizing As (III) based on iron ion system alone

First, 50mL of As (III) solution was taken in a 100 mL-volume Erlenmeyer flask, and the solution was left to stir at room temperature. And (3) transferring 50 mu L of iron salt stock solution by using a precision pipettor, adding the iron salt stock solution into the conical flask, starting timing, transferring 4mL of iron salt stock solution by using the pipettor every 10s within 10s-60s, quickly adding the iron salt stock solution into 2% hydrochloric acid and the color developing agent prepared in the example 2, and then detecting the absorbance of As (V) in the water body by using an ultraviolet-visible spectrophotometer. According to the measured absorbance of As (V) in the water body, the concentration of As (V) is found on the standard curve of the content of As (V) in example 2, and the result is shown in FIG. 4.

Comparative example 15 method for removing As (V) based on iron ion system alone

First, 50mL of As (V) solution was taken in a 100 mL-volume Erlenmeyer flask, and the solution was left to stir at room temperature. And (3) transferring 50 mu L of iron salt stock solution into the conical flask by using a precision pipettor, starting timing, transferring 1mL of water in the conical flask by using the pipettor every 10s within 10s-60s, rapidly passing through a 0.22 mu m water system filter membrane, and detecting a response value of a residual total arsenic signal in the filtered water by using an inductively coupled plasma mass spectrometer. According to the measured signal response value of the total arsenic remaining in the water body, the concentration of the total arsenic remaining in the water body is found on the standard curve of the total arsenic in the water body in example 1, and the result is shown in fig. 6.

FIG. 1 is a graph showing the effect of example 1, comparative example 1 and comparative example 7 on the removal of As (III); as can be seen from FIG. 1, the removal effect of the ferrous ion-coupled peroxymonosulfate system on As (III) is significantly better than that of the ferrous ion-coupled peroxydisulfate system and the ferrous ion-coupled hydrogen peroxide system.

FIG. 2 is a graph showing the oxidation effects of example 2, comparative example 2 and comparative example 8 on As (III); as can be seen from FIG. 2, the oxidation effect of the ferrous ion-coupled peroxymonosulfate system on As (III) is significantly better than that of the ferrous ion-coupled peroxydisulfate system and the ferrous ion-coupled hydrogen peroxide system.

FIG. 3 is a graph showing the effect of example 3, comparative example 9 and comparative example 13 on the removal of As (III); as can be seen from fig. 3, the removal effect of the iron ion-coupled peroxymonosulfate system on as (iii) is significantly better than that of the iron ion-coupled peroxydisulfate system, the iron ion-coupled hydrogen peroxide system, and the iron ion system alone.

FIG. 4 is a graph showing the oxidation effects of example 4, comparative example 10, and comparative example 14 on As (III); as can be seen from fig. 4, the oxidation effect of the iron ion-coupled peroxymonosulfate system on as (iii) is significantly better than that of the iron ion-coupled peroxydisulfate system, the iron ion-coupled hydrogen peroxide system, and the iron ion system alone.

FIG. 5 is a graph showing the effect of example 5, comparative example 5 and comparative example 11 on the removal of As (V); as can be seen from fig. 5, the removal effect of the ferrous ion coupled peroxymonosulfate system on as (v) is significantly better than that of the ferrous ion coupled peroxydisulfate system and the ferrous ion coupled hydrogen peroxide system.

FIG. 6 is a graph showing the effect of example 6, comparative example 12 and comparative example 15 on the removal of As (V); as can be seen from fig. 6, the removal effect of the iron ion-coupled peroxymonosulfate system on as (v) is significantly better than that of the iron ion-coupled peroxydisulfate system, the iron ion-coupled hydrogen peroxide system, and the iron ion system alone.

As can be seen from FIGS. 1-6, the system of ferrous ion or ferric ion coupled with monopersulfate has better effect on the oxidation of As (III). As (III) is known to be more difficult to adsorb and remove than As (V). The excellent oxidation effect of the ferrous or ferric ion coupled persulfate system on As (III) leads to the excellent removal effect of As (III) in the system.

FIG. 7 is a graph showing the effect of example 7 on the removal of As (III). As can be seen from fig. 7, the higher the ferrous ion concentration, the higher the total arsenic removal rate. When the ferrous ion continued to increase to 500 μ M, there was a slight decrease in removal rate, but still above 90%.

FIG. 8 is a graph showing the effect of example 8 on the removal of As (III). As can be seen from fig. 8, the higher the peroxymonosulfate concentration, the higher the total arsenic removal.

FIG. 9 is a graph showing the effect of example 9 on the removal of As (III). As can be seen from FIG. 9, the removal rate gradually decreases as the initial concentration of As (III) increases, and both the removal rates are higher than 90% in the initial concentration range of As (III) from 0.2 mg/L to 2mg/L, and still reach 87.6% when the initial concentration of As (III) increases to 5 mg/L.

FIG. 10 is a graph showing the effect of example 10 on the removal of As (V). As can be seen from fig. 10, as (v) removal rate increases with increasing ferrous ion concentration, and as the ferrous ion concentration continues to increase to 500 μ M, the removal rate slightly decreases, but still is higher than 98%.

FIG. 11 is a graph showing the effect of example 11 on the removal of As (V). As can be seen from FIG. 11, As (V) removal rate increases with increasing concentration of peroxymonosulfate.

FIG. 12 is a graph showing the effect of example 12 on the removal of As (V). As can be seen from FIG. 12, the removal rate gradually decreases as the initial As (V) concentration increases, and is higher than 98% in the initial As (V) concentration range of 0.2-2mg/L, and still reaches 60% when the initial As (V) concentration increases to 5 mg/L.

FIG. 13 is a graph showing the effect of example 13 on the removal of As (III). As can be seen from fig. 13, the total arsenic removal rate increases with increasing iron ion concentration, and when the iron ion concentration continues to increase to 500 μ M, the removal rate slightly decreases, but still is higher than 90%.

FIG. 14 is a graph showing the effect of example 14 on the removal of As (III). As can be seen from fig. 14, the total arsenic removal rate increases with increasing concentration of the monopersulfate.

FIG. 15 is a graph showing the effect of example 15 on the removal of As (III). As can be seen from FIG. 15, the higher the initial As (III) concentration is, the removal rate gradually decreases, the removal rate is higher than 98% in the initial As (III) concentration range of 0.2-2mg/L, and the removal rate is still as high as 60% when the initial As (V) concentration is increased to 5 mg/L.

FIG. 16 is a graph showing the effect of example 16 on the removal of As (V). As can be seen from fig. 16, as (v) removal rate increases with increasing iron ion concentration, and as the iron ion concentration continues to increase to 500 μ M, the removal rate slightly decreases, but still is higher than 90%.

FIG. 17 is a graph showing the effect of example 17 on the removal of As (V). As can be seen from FIG. 17, As (V) removal rate increases with increasing concentration of peroxymonosulfate.

FIG. 18 is a graph showing the effect of example 18 on the removal of As (V). As can be seen from FIG. 18, the removal rate gradually decreased as the initial As (V) concentration was higher, and was higher than 98% in the initial As (V) concentration range of 0.2-1.5mg/L, and still reached 80% when the initial As (V) concentration was increased to 2mg/L, and still reached 60% when the initial As (V) concentration was increased to 5 mg/L.

Example 19

First, 50mL of deionized water was taken in a 100mL conical flask and the solution was placed under stirring at room temperature. Respectively transferring 50 mu L of ferrous or ferric salt stock solution and 75 mu L of oxidant stock solution by a precision pipettor, simultaneously adding the ferrous or ferric salt stock solution and the oxidant stock solution into the conical flask, stirring for 60s, and then determining the particle size of the floccule on a Malvern laser particle size analyzer. The results are shown in FIG. 19, which is a graph of the average particle size of flocs formed by different systems in FIG. 19. As can be seen from fig. 19, the flocs generated by the coupling of ferrous or ferric ions to the monosulfate have smaller sizes and therefore more adsorption sites resulting in better removal of as (iii) and/or as (v).

Claims

1. A method for enhancing removal of As (III) and/or As (V) based on coupling of ferrous ions or ferric ions with peroxymonosulfate is characterized in that ferrous salt solution or ferric salt solution and peroxymonosulfate solution are added into a water body containing As (III) and/or As (V), stirring is carried out at normal temperature for reaction, and filtering is carried out, so that removal of As (III) and/or As (V) can be completed.

2. The method for enhancing the removal of As (III) and/or As (V) based on the ferrous or ferric ion coupled peroxymonosulfate as claimed in claim 1, wherein the reaction time of stirring at normal temperature is 10-60 s.

3. The method for enhancing removal of As (III) and/or As (V) based on ferrous or ferric ion coupled peroxymonosulfate as claimed in claim 1, wherein the concentration of As (III) and/or As (V) in the body of water is 0.2-5.0 mg/L.

4. The method of claim 1, wherein the pH of the body of water is greater than 3.7.

5. The method for enhancing As (III) and/or As (V) removal based on ferrous or ferric ion coupled peroxymonosulfate as claimed in claim 1, wherein the concentration of the added ferrous salt solution or ferric salt solution in the water body is 62.5-500 μ M.

6. The method for enhancing As (III) and/or As (V) removal based on ferrous or ferric ion coupled monopersulfate according to claim 1, wherein the added monopersulfate solution is present in the water at a concentration of 16-320 μ M.