CN110745982B - Method for deep oxidation treatment of organic wastewater based on visible light assisted complexing iron ion activated monoperoxybisulfate - Google Patents

Method for deep oxidation treatment of organic wastewater based on visible light assisted complexing iron ion activated monoperoxybisulfate Download PDF

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CN110745982B
CN110745982B CN201910864471.XA CN201910864471A CN110745982B CN 110745982 B CN110745982 B CN 110745982B CN 201910864471 A CN201910864471 A CN 201910864471A CN 110745982 B CN110745982 B CN 110745982B
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pms
oxalate
wastewater
codcr
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CN110745982A (en
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韩东晖
李瑛�
吴仁人
任秀文
陈晨
荣楠
廖文
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South China Institute of Environmental Science of Ministry of Ecology and Environment
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F2001/007—Processes including a sedimentation step
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/101—Sulfur compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

A method for deep oxidation treatment of organic wastewater based on visible light assisted complexing iron ion activated monoperoxybisulfate. The method comprises the following steps: adding PMS into the initial organic wastewater, fully mixing, adding a mixed solution of oxalate and ferric salt, irradiating by using an LED lamp, synchronously stirring for reaction, adding alkali liquor and calcium hydroxide, uniformly stirring, precipitating, and effectively reducing CODcr in the supernatant tail water. According to the method, under the condition that the initial pH of the wastewater is not adjusted, the iron ion precipitation is controlled through a complexing agent, the ferrous ions are promoted to be circularly generated under the action of visible light, PMS is continuously catalyzed and activated to generate strong oxidizing sulfate radicals, organic pollutants are effectively oxidized and degraded, and the CODcr in the wastewater is efficiently removed. The method has the characteristics of strong operability, low energy consumption, wide pH application range, good oxidation reaction continuity, high organic matter oxidation degradation efficiency and the like, and has great application potential in the field of advanced wastewater treatment.

Description

Method for deep oxidation treatment of organic wastewater based on visible light assisted complexing iron ion activated monoperoxybisulfate
Technical Field
The invention belongs to the technical field of water pollution control, and particularly relates to a method for deeply oxidizing organic wastewater based on visible light assisted complexing iron ion activated hydrogen monoperoxysulfate (PMS).
Background
In recent years, water treatment technologies based on radical oxidation of sulfate have attracted increasing attention. Sulfate radicals have a very strong oxidizing power (E) 0 2.5-3.1V), can be generated by catalytically activating persulfate or PMS by light, heat, electrochemistry, transition metals and the like, and has good effect on the advanced treatment of organic wastewater.
In the activity of numerous persulfates or PMSIn the chemical formula, based on Fe 2+ The activation mode not only shows better activation effect, but also has the advantages of low cost, environmental friendliness and the like, and is the best activation mode for the actual wastewater treatment process. But based on Fe 2+ The mode of activation still presents some problems, firstly Fe 2+ Is easily oxidized into Fe 3+ Thereby quickly losing the activation effect, causing the activation process of persulfate or PMS to be very short and the sulfate radical can not be continuously generated; second Fe added in wastewater 2+ Can quickly react with the oxidative free radicals generated by activation, consume the free radicals, reduce the utilization efficiency of the oxidant and influence the oxidation removal efficiency of pollutants. For this reason, in recent years, around solving the problems of persistent activation of iron ions and radicals, etc., some heterogeneous activators (CN105110448B, CN105217773B), complex iron ions (CN103435143A), etc. have appeared as iron ion-based activation methods. However, the above complexing method can increase Fe 2+ The removal efficiency of catalytically activating persulfate or PMS to oxidatively degrade refractory organic matters still has the following problems: (1) the iron ion release process of the heterogeneous iron-based activator is slow, the surface of the solid-phase catalyst is easy to passivate or agglomerate to reduce the activity performance, so that the catalytic activation efficiency in the actual wastewater treatment process is low, and meanwhile, the solid-phase catalyst also has the problems of difficult recovery or poor recycling effect. (2) The activation mode of complex iron ions improves Fe to a certain extent 2+ Problem of fast consumption, but with Fe 2+ The persulfate or PMS activation effect is reduced continuously.
The invention discloses a method for advanced oxidation treatment of organic wastewater based on visible light assisted complexing iron ion activated PMS, which is a homogeneous reaction process, can effectively solve the problems existing in the heterogeneous catalytic activation reaction process, simultaneously utilizes the complexing and photosensitive properties of oxalate ions and adopts Fe 3+ As an activator, promoting Fe in a complex state by visible light 3+ Cyclic conversion to produce Fe 2+ Realizes the continuous activation of PMS to generate sulfate radicals, and solves the problem of poor continuous effect of homogeneous catalytic activation based on iron ionsThe method effectively improves the efficiency of treating organic wastewater by using single complexing catalytic activated persulfate or PMS.
Disclosure of Invention
The invention aims to solve the problem of conventional Fe 2+ In the process of treating organic wastewater by activating PMS, Fe is used 2+ Is easily oxidized to form Fe 3+ The PMS can not be continuously activated to generate oxidizing free radicals, so that the problem of low removal efficiency of the organic wastewater CODcr is caused.
The invention discloses a method for advanced oxidation treatment of organic wastewater based on visible light assisted complexing iron ion activated PMS, which uses oxalate ions to complex Fe 3+ Promoting Fe under the action of visible light 2+ And (3) cyclic generation is carried out, so that PMS is continuously and effectively activated to generate sulfate radical free radicals, organic pollutants in the wastewater are efficiently removed, and removal of sulfate ions and effective separation of iron mud are realized by a mode of subsequently adding alkali liquor and calcium hydroxide. The method has strong adaptability to the pH value of the wastewater, is easy to operate, has good CODcr removing effect, and compares the prior Fenton and Fe when carrying out advanced treatment on the complex organic wastewater 2+ The method for activating persulfate, PMS and the like has obvious advantages.
The technical scheme for realizing the purpose of the invention is as follows:
a method for deep oxidation treatment of organic wastewater based on visible light assisted complexing of iron ion activated hydrogen monoperoxysulfate comprises the following steps:
(1) measuring the CODcr value of the organic wastewater to be treated, wherein the organic wastewater is wastewater containing one or more organic substances, and the CODcr is less than or equal to 100 mg/L;
(2) selecting the adding amount of PMS, trivalent ferric salt and oxalate according to the CODcr value measured in the step (1);
the dosage of PMS increases with the increase of CODcr, and PMS (mg/L, HSO) is controlled 5 - ) The ratio of the active component to CODcr (mg/L) is 10/1-20/1; the dosage of the trivalent ferric salt and the trivalent oxalic salt is increased along with the increase of the dosage of PMS, and PMS (mol/L, HSO) is controlled 5 - ) With Fe 3 + The ratio of (mol/L) is 10/1-25/1, and the oxalate ion (mol/L) and Fe are controlled 3 + The concentration ratio of (mol/L) is 2/1-5/1;
(3) putting the wastewater to be treated in the step (1) into a beaker, adding the PMS with the determined adding amount in the step (2), and fully mixing;
(4) sequentially adding the trivalent ferric salt and oxalate mixed solution with the adding amount determined in the step (2) into the beaker in the step (3), and uniformly stirring;
(5) starting a visible light source, irradiating the beaker in the step (4), and reacting for 1-2 hours;
(6) and (5) adding an alkaline solution and calcium hydroxide into the beaker in the step (5), fully mixing, and standing for precipitation.
Further, in the step (2), the PMS is more than one of sodium monoperoxysulfate, potassium monoperoxysulfate and ammonium monoperoxysulfate; the ferric iron salt is more than one of ferric sulfate, ferric chloride and ferric nitrate; the oxalate comprises more than one of oxalic acid, sodium oxalate, calcium oxalate, iron potassium oxalate and ammonium oxalate.
Further, in the step (5), the visible light is light emitted by any one of a metal halide lamp, a xenon lamp, and an LED lamp.
Further, in the step (6), the alkaline solution is an aqueous solution containing one or more of sodium hydroxide and potassium hydroxide.
Further, in the step (6), the adding amount of the alkali liquor needs to control the pH value of the mixed solution to be 8-9.
Further, in the step (6), the amount of calcium hydroxide added is increased with the increase of the amount of PMS added, and PMS (mol/L, HSO) is controlled 5 - ) The concentration ratio of the calcium hydroxide to the calcium hydroxide (mol/L) is 1/2-1/6.
Further, in the step (6), the standing and precipitating time is 1-3 hours.
Compared with the prior art, the invention has the following advantages:
(1) compared with other oxidants such as hydroxyl radical and the like, the sulfate radical based on the method has stronger oxidizing capability and no selectivity to organic pollutants, so that the method has better CODcr removing effect when the complex organic wastewater is subjected to advanced treatment.
(2) Compared with the traditional persulfate, the PMS adopted in the invention is more easily activated to generate sulfate radicals, so that compared with a persulfate activation method, the PMS disclosed by the invention has higher efficiency of generating sulfate radicals by activating.
(3) In the invention, the PMS activation process is an acid production process, the pH of the reaction system is gradually reduced along with the activation reaction, so that the method has good adaptability to high-pH wastewater, and compared with a Fenton process, the method does not need to pre-adjust the acid of the neutral and alkaline wastewater, so that the operation is simpler and the treatment cost can be reduced.
(4) The activator of PMS in the present invention is Fe 3+ Is more stable in the actual water treatment process, and Fe is used in the reaction process related to the invention 3+ With Fe 2+ The PMS can be continuously and circularly generated, and the PMS can be continuously activated to generate sulfate radicals. Thus, compared with conventional Fe 2+ Or complexing Fe 2+ The PMS activation method not only can more efficiently activate PMS to oxidize and remove CODcr, but also can effectively reduce the initial PMS, the adding amount of ferric salt and the generation amount of iron mud, and reduce the treatment cost.
(5) The invention adopts the visible light source as the assistant, and has lower requirements on the operating conditions and the cost compared with the conventional ultraviolet light assistant method.
(6) According to the invention, calcium hydroxide is used as a sulfate ion remover, so that the concentration of sulfate ions in the treated wastewater can be effectively reduced. Meanwhile, when ferric chloride is used as the ferric salt, the ferric chloride can be used as a coagulant in the precipitation stage, so that the flocculation precipitation effect is enhanced, and the effective separation of mud and water is realized.
Drawings
FIG. 1 is a process flow diagram of the method of the present invention.
Detailed Description
The present invention is described in further detail below by way of examples, but the scope of the present invention is not limited to the following examples.
The process flow of the following examples is detailed in FIG. 1.
Example 1
250mL of aniline solution with CODcr of 200mg/L, pH ═ 5 are respectively put into 6 beakers under the condition of normal temperature, and are respectively marked as 1#, 2#, 3#, 4#, 5#, and 6 #.
(1) Adding PMS solution into a No. 1 beaker, uniformly mixing, simultaneously starting an LED light source to irradiate the solution in the beaker, timing when the reaction is started, adding a proper amount of alkali liquor and calcium hydroxide after reacting for 2 hours, and standing for 1 hour;
(2) firstly adding PMS solution into a No. 2 beaker, uniformly mixing, then adding ferric chloride solution, timing when the reaction is started, adding a proper amount of alkali liquor and calcium hydroxide after the reaction is carried out for 2 hours, and standing for 1 hour;
(3) adding PMS into a No. 3 beaker, uniformly mixing, then adding a fresh prepared ferrous sulfate solution, timing when the reaction is started, adding a proper amount of alkali liquor and calcium hydroxide after the reaction is carried out for 2 hours, and standing for 1 hour;
(4) adding PMS into a No. 4 beaker, uniformly mixing, then adding a freshly prepared mixed solution of oxalic acid and ferrous sulfate, timing when the reaction is started, adding a proper amount of alkali liquor and calcium hydroxide after reacting for 2 hours, and standing for 1 hour;
(5) firstly adding PMS into a No. 5 beaker, uniformly mixing, then adding a freshly prepared oxalic acid and ferrous sulfate mixed solution, simultaneously starting an LED light source to irradiate the solution in the beaker, timing when the reaction starts, adding a proper amount of alkali liquor and calcium hydroxide after reacting for 2 hours, and standing for 1 hour;
(6) firstly adding PMS into a No. 6 beaker, uniformly mixing, then adding a freshly prepared oxalic acid and ferric chloride mixed solution, simultaneously starting an LED light source to irradiate the solution in the beaker, timing when the reaction starts, adding a proper amount of alkali liquor and calcium hydroxide after reacting for 2 hours, and standing for 1 hour;
the volume of the beaker No. 1 to No. 6 was controlled to be 500mL after all the solution was added, at which time the COD concentration was 100 mg/L. Control of PMS (mg/L, KHSO) 5 ) The concentration ratio of the active carbon to CODcr (mg/L) is 15/1, PMS (mol/L, KHSO) 5 ) The concentration ratio of the oxalate ion to the iron ion (mol/L) is 15/1, the concentration ratio of the oxalate ion to the iron ion (mol/L) is 3/1, and the concentration ratio of PMS (mol/L, KHSO) 5 ) The ratio of the concentration of calcium hydroxide (mol/L) was 1/4, and the pH during the precipitation was adjusted to 8.5. In this embodiment, the PMS adopts a single-pass modePotassium hydrogen oxysulfate complex salt (2 KHSO) 5 ·KHSO 4 ·K 2 SO 4 ) (ii) a The alkali liquor is 30% NaOH solution.
The results are shown in table 1, and the results show that the method for treating organic wastewater by advanced oxidation through visible light assisted complexing iron ion activated PMS, which is established by the invention, can more effectively remove CODcr in wastewater compared with other methods, and compared with a PMS/ferrous sulfate/oxalic acid/LED treatment method, the removal amount of CODcr generated by unit PMS activation decomposition amount is higher, which shows that the utilization efficiency of sulfate radicals generated by PMS activation by organic pollutants is higher, and when the same CODcr removal rate is realized, the initial PMS addition amount required by the method is lower.
TABLE 1 treatment of aniline wastewater by PMS oxidation in different ways
Figure BDA0002200847940000051
Example 2
250mL of aniline solution with CODcr of 200mg/L, pH ═ 10 were placed in 3 beakers at room temperature, and labeled 1#, 2#, 3#, and 4#, respectively.
(1) Firstly adding PMS into a No. 1 beaker, uniformly mixing, then adding a fresh prepared ferrous sulfate solution, timing when the reaction starts, adding alkali liquor and calcium hydroxide after reacting for 2 hours, and standing for 1 hour;
(2) adding PMS into a No. 2 beaker, uniformly mixing, then adding a freshly prepared mixed solution of oxalic acid and ferrous sulfate, timing when the reaction is started, adding alkali liquor and calcium hydroxide after reacting for 2 hours, and standing for 1 hour;
(3) adding PMS into a No. 3 beaker, uniformly mixing, then adding a freshly prepared mixed solution of oxalic acid and ferrous sulfate, starting an LED light source to irradiate the solution in the beaker, starting reaction for timing, adding alkali liquor and calcium hydroxide after reacting for 2 hours, and standing for 1 hour;
(4) adding PMS into a No. 4 beaker, uniformly mixing, then adding a freshly prepared oxalic acid and ferric chloride mixed solution, starting an LED light source to irradiate the solution in the beaker, starting reaction for timing, adding alkali liquor and calcium hydroxide after reacting for 2 hours, and standing for 1 hour;
the volume of the beaker No. 1 to No. 4 was controlled to be 500mL after all the solution was added, and the COD concentration at this time was 100 mg/L. Control of PMS (mg/L, KHSO) 5 ) The concentration ratio of the active carbon to CODcr (mg/L) is 15/1, PMS (mol/L, KHSO) 5 ) The concentration ratio of the oxalate ion to the iron ion (mol/L) is 15/1, the concentration ratio of the oxalate ion to the iron ion (mol/L) is 3/1, and the concentration ratio of PMS (mol/L, KHSO) 5 ) The ratio of the concentration of calcium hydroxide (mol/L) was 1/4, and the pH during the precipitation was adjusted to 8.5. In this example, PMS was prepared from potassium monoperoxysulfate complex salt (2 KHSO) 5 ·KHSO 4 ·K 2 SO 4 ) (ii) a The alkali liquor is 30% NaOH solution.
The results are shown in table 2, and the results show that the method for treating organic wastewater by deep oxidation by activating PMS through visible light assisted complexing iron ions, which is established by the invention, has a lower removal effect on CODcr in wastewater than that under the condition of lower initial pH (example 1), but PMS can still be effectively activated at the moment, and the removal rate of CODcr can reach nearly 60% and is obviously higher than that of other treatment methods.
TABLE 2 treatment of aniline wastewater by PMS activation in different ways
Figure BDA0002200847940000061
Example 3
250mL of aniline solution with CODcr of 200mg/L, pH ═ 7 were placed in 2 beakers at room temperature, and labeled as # 1 and # 2, respectively.
The PMS in the embodiment adopts KHSO 5 。
(1) Firstly adding PMS into a No. 1 beaker, uniformly mixing, then adding a freshly prepared oxalic acid and ferric chloride mixed solution, simultaneously starting an LED light source to irradiate the solution in the beaker, timing when the reaction starts, adding alkali liquor after the reaction is carried out for 2 hours, and standing for 1 hour;
(2) firstly adding PMS into a No. 2 beaker, uniformly mixing, then adding a freshly prepared oxalic acid and ferric chloride mixed solution, starting an LED light source to irradiate the solution in the beaker, starting reaction for timing, adding alkali liquor and calcium hydroxide after reacting for 2 hours, and standing for 1 hour;
the volume of the beaker No. 1-2 was controlled to be 500mL after all the solution was added, at which time the COD concentration was 100 mg/L. Control of PMS (mg/L, KHSO) 5 ) The concentration ratio of the active carbon to CODcr (mg/L) is 15/1, PMS (mol/L, KHSO) 5 ) The concentration ratio of the oxalate ion to the iron ion (mol/L) is 15/1, the concentration ratio of the oxalate ion to the iron ion (mol/L) is 3/1, and the concentration ratio of PMS (mol/L, KHSO) 5 ) The ratio of the concentration of calcium hydroxide (mol/L) was 1/4, and the pH during the precipitation was adjusted to 8.5. In this example, PMS was prepared from potassium monoperoxysulfate complex salt (2 KHSO) 5 ·KHSO 4 ·K 2 SO 4 ) (ii) a The alkali liquor is 30% NaOH solution.
The results are shown in table 3, and the results show that the method for treating organic wastewater by advanced oxidation through visible light assisted complexing iron ion activated PMS, which is established by the invention, can effectively reduce the content of sulfate ions in the supernatant tail water by adding alkali liquor and calcium hydroxide after the reaction is finished, and solve the problem of standard exceeding of the concentration of the sulfate ions.
TABLE 3 sulfate concentration of tail water in different soda adjusting modes
Figure BDA0002200847940000071

Claims (1)

1. A method for deep oxidation treatment of organic wastewater based on visible light assisted complexing iron ion activated monoperoxybisulfate is characterized by comprising the following steps: the method comprises the following steps:
(1) measuring the CODcr value of the organic wastewater to be treated, wherein the organic wastewater is wastewater containing one or more organic substances, and the CODcr is less than or equal to 100 mg/L;
(2) selecting the adding amount of PMS, trivalent ferric salt and oxalate according to the CODcr value measured in the step (1);
the dosage of PMS increases with the increase of CODcr, and PMS (mg/L, HSO) is controlled 5 - ) The ratio of the active component to CODcr (mg/L) is 10/1-20/1; the dosage of the trivalent ferric salt and the dosage of the oxalate are along with PThe amount of MS is increased to control PMS (mol/L, HSO) 5 - ) With Fe 3+ The ratio of (mol/L) is 10/1-25/1, and the oxalate ion (mol/L) and Fe are controlled 3+ The concentration ratio of (mol/L) is 2/1-5/1;
(3) putting the wastewater to be treated in the step (1) into a beaker, adding the PMS with the determined adding amount in the step (2), and fully mixing;
(4) sequentially adding the trivalent ferric salt and oxalate mixed solution with the adding amount determined in the step (2) into the beaker in the step (3), and uniformly stirring;
(5) starting a visible light source, irradiating the beaker in the step (4), and reacting for 1-2 hours;
(6) adding an alkaline solution and calcium hydroxide into the beaker in the step (5), fully mixing, and standing for precipitation;
in the step (2), the PMS is more than one of sodium monoperoxysulfate, potassium monoperoxysulfate and ammonium monoperoxysulfate; the ferric iron salt is more than one of ferric sulfate, ferric chloride and ferric nitrate; the oxalate comprises more than one of oxalic acid, sodium oxalate, calcium oxalate, iron potassium oxalate and ammonium oxalate;
in the step (5), the visible light is light emitted by any one of a metal halide lamp, a xenon lamp and an LED lamp;
in the step (6), the adding amount of the calcium hydroxide is increased along with the increase of the adding amount of PMS, and the concentration ratio of PMS (mol/L, HSO 5-) to calcium hydroxide (mol/L) is controlled to be 1/2-1/6;
in the step (6), the alkaline solution is an aqueous solution containing more than one of sodium hydroxide and potassium hydroxide;
in the step (6), the adding amount of the alkali liquor needs to control the pH value of the mixed solution to be 8-9;
in the step (6), the standing and precipitating time is 1-3 hours.
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